Geochemische Methoden

Rock Eval Pyrolysis Rock eval pyrolysis is a method to analyze maturity and potential of a possible source rock.
Therefore 100mg of the pulverized sample was burned in an inert helium atmosphere. First it was heated fast up to 300 C to vaporize all free hydrocarbons that are already present by generation since the deposition. They are measured by a flame ionisation detector (FID) and illustrated as a peak and its area S1. Then the temperature was steadily raised 25 C/min up to 550 C. At this temperature all remaining kerogen has been cracked. The now generated hydrocarbons are shown in another peak with the area S2. S3 representing the carboxyl groups that originate from the kerogen at temperatures between 300 C and 390 C and are measured during the cooling process by a thermal conductivity detector (TCD), could not be generated. (Killops & Killops 2005) We can create parameters with S1 and S2 that indicate us maturity, quality and potential for oil generation of the kerogen in our samples. Tmax is the peak of S2 and describes the maximum temperature when the remaining kerogen was cracked and the maximum liberation of hydrocarbons was reached. The hydrogen index (HI) value tells us the content of hydrocarbons in milligrams per gram TOC (mg HC/g TOC) that are achieved by cracking the kerogen and thereby the grade of preservation of hydrogen-rich and possibly oil-prone organic matter (Littke 1993). While a high value indicates anoxic deposition conditions, a low value indicates terrestrial sources of organic matter or that already hydrocarbons were formed. It is computed by the formula (S2/TOC) x 100. Another parameter for maturity is the production index (PI) value with the formula S1/(S1+S2). PI and Tmax both increase with advanced generation of hydrocarbons and temperature. (Hunt 1995)
N-alkanes Cleaning of the used implements and purity of the solvents Only implements consisting of the materials glass, special steel and teflon were used for the laboratory activities. The utensils were cleaned with hot water and dish liquid until there was no pollutant visible to the naked eye. Afterwards the implements were soaked in a washtub for at least one night before they were put into a dish washer. After that they were dried in a cabinet dryer by 100C for at least one hour. Close to their utilization they were rinsed first with hexane to eliminate all polar matter. All solvents were produced and checked for purity by the in-house laboratory.
Extraction Organic matter was disassociated from the samples via ultrasound extraction.
Therefore 10g of material of a sample were weighed first in a round bottom flask and then mixed with 40ml of dichloromethane. Afterwards the round bottom flask was given in an ultrasound bath for 15 minutes. After a following intermission of 15 minutes the flask was hanged for another 15 minutes into the ultrasound bath. The warmth and the energy that are conducted with the bath facilitate the loosening of the components. Subsequently a magnetic stir bar was given to the sample which was kept moving on a magnetic stirrer over night. On the next day the sample was filtered through a glass funnel with filter paper into a second round bottom flask. The residue was given back into the first flask and was mixed with 40ml hexane. Now the flask was hanged again in an ultrasound bath for two times 15 minutes with a 15 minutes break in between. After that the content was filtered through the same filter into the second flask. Parallel to this procedure copper powder consisting of pure elemental copper was activated for a few hours in hydrochloride acid. The copper was now added to the filtrated solution. It reacts with in the sample existent sulphur to copper sulphide compounds (mostly covellite CuS), so the sulphur cannot interfere in the following measurements. The sample with the copper was stored in a refrigerator for one night. On the next day the solution was boiled down to ca. 5ml in a rotary evaporator in a vacuum with 300 mbar in a bath with a temperature of 30C.
Fractionation The organic components in the solution that was obtained from the extraction, were now separated after their polarity via fractionation. Thereby fractions of increasing polarity were eluted with in each case 5ml of three increasingly polar solvents. To prepare the fractionation one bakerbond column for each sample was packed with 2g silica gel between two teflon frits. These were conditioned over night in a cabinet dryer by 200C. Thereafter the column was saturated with pentane until there was no air in the silica gel left. Now the sample was poured into the column. The flask was rinsed with 1ml pentane, which was also poured into the flask. After the total absorption, the three solvents with different polarity were applied. For the first fraction, the aliphatic compounds, pentane was used. Therefore just 4ml were taken because 1ml was already used to rinse the flask. For the second fraction, the aromatic hydrocarbons, an alloy of DCM-hexane at the ratio of 40:60 and for the third fraction, the NSOcompounds, methanol was used. After they run through the column, the different fractions were collected in 8ml flasks. These solutions were boiled down with a nitrate evaporator to 1ml for the subsequent described gas chromatography.
Gas chromatography with a flame ionisation detector (FID) Gas chromatography is a physical-chemical analysis technique, by which the substances to be analyzed are separated by being distributed on two non-mixable phases.
The first phase is called stationary. It sticks as a thin layer on the inner surface of a capillary column which presents the isolating distance. In our case silica gel is used. The mobile phase, H2 was used, transports our sample as a carrier gas. During injection the sample was vaporized by 300 C. After different periods of remaining in the stationary phase (called retention time) the constituent parts of the sample reach the detector, which is in our case a flame ionization detector (FID). In its H2-flame the substances to be detected with C-H or C-C bonds get burned, pyrolized and oxidized by OH radicals that developed in the flame. The oxidation products get ionized by their excitation energy. In the process electrons get discharged which are detected as peaks with different altitudes and areas which represent different n-alkanes and their occurrence in the sample. (Hbschmann 2009; Kolb 1999) The preference for even or odd n-alkanes can be used as an indicator for maturity. Therefore helps the carbon-preference-index (CPI) or the odd-to-even predominance (OEP) value. The formula for the OEP used in this thesis is OEP=(C21+6C23+C25)/(4C22+4C24). (Peters et al. 2004)

Geochemische Methoden

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Rock Eval Pyrolysis Rock eval pyrolysis is a method to analyze maturity and potential of a possible source rock.

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