Geothermometry by Raman spectroscopy of dispersed organic matter

Raman-Spektroskopie an kohligem Material (RSCM) ist eine häufig verwendete Methode, um die maximale Temperatur der Metamorphose oder die thermische Reife von Kohlen und organikreichen Sedimenten zu bestimmen. Für die Temperaturabschätzung wurden bereits mehrere Kalibrationskurven ermittelt, jedoch wird die Übertragbarkeit dieser Kalibrationen auf andere Labore durch methodische Aspekte eingeschränkt und die Vergleichbarkeit zwischen den Laboren dadurch reduziert. Die subjektive Auswertung von Spektren, das verwendete Messsystem und die Probenheterogenität bedingen die größte Streuung der Ergebnisswerte und ein Ansatz, mit dem Ziel die Vergleichbarkeit zu erhöhen, wurde formuliert. Um die Subjektivität der spektralen Auswertung zu veringern, wurde das ’IFORS’ (Iterative Fitting Of Raman Spectra) Programm geschrieben, das die automatische, Benutzer-unabhängige Auswertung von Raman-Spektren ermöglicht. Um die Streuung aufgrund des verwendeten Messsystems zu reduzieren, wurde ein Referenzprobensatz zusammengestellt, der einen Temperaturbereich von 160 °C bis 600 °C abdeckt. Während der Probenaufbereitung wurde Resonanz-Raman- Spektroskopie mit mehreren Anregungswellenlängen an dispersen Vitriniten durchgeführt, die diagenetische bis epizonale Druck- und Temperaturbedingungen erfahren hatten, um die Gleichwertigkeit der RSCM-Methode und Vitrinitreflexion zu ermitteln. Mit Hilfe des IFORS Programms wurde der ’scaled total area’ (STA) Raman Parameter ermittelt, der das Raman Spektrum von kohligem Material präzise beschreibt. Auf Grundlage der Resonanz-Raman Daten konnte gezeigt werden, dass die Methodiken der STA-Raman Spektroskopie und Vitrinitreflexion analog zueinander sind, dass die STA-RSCM Methode gegenüber der Probenaufbereitung, insbesondere dem Polieren, robust ist, und dass die Resonanz-Raman Spektren der Vitrinite eine zweistufige molekulare Entwicklung während der Inkohlung und Graphitisierung aufzeichnen. Während der ersten Stufe, die kurz nach dem Durchschreiten des Gas-Fensters endet, wachsen vor allem lineare, polyzyklische, aromatische Kohlenwasserstoffe, während in der anschließenden zweiten Stufe kondensierte Formen von polyzyklischen, aromatischen Kohlenwasserstoffen wachsen. Um die Raman Spektren von metamorphem, kohligem Material zu beschreiben, wurde die STA-RSCM Methodik erweitert und erfolgreich gegen die Temperaturinformation des Referenzprobensatzes kalibriert, so dass ein neues, überarbeitetes RSCM-Geothermometer vorgestellt werden konnte, das über einen Temperaturbereich von 160°C bis 600°C zulässig ist. Der Referenzprobensatz steht öffentlich zur Verfügung und es wird erwartet, dass der Probensatz verbessert werden kann, wenn er um Proben aus der wissenschaftilchen Gemeinschaft erweitert wird. Wenn beide Ansätze, die STA-RSCM Methodik und der Referenzprobensatz, miteinander kombiniert werden, erhöht sich die Vergleichbarkeit zwischen den Laboren und gleichzeitig steht diese geothermometrische Methode allen Laboren zur Verfügung.Raman spectroscopy of carbonaceous material (RSCM) is frequently used to determine peak metamorphic temperature or to infer the coal rank as well as the degree of organic maturation. Several temperature calibrations exist, but methodical aspects limit the portability of these calibrations among laboratories and reduce overall comparability of the method. By identifying the subjectivity of spectral evaluation, experimental setup and sample heterogeneity as major sources of bias in the method, an outline to increase comparability could be established. To reduce the subjectivity during spectral evaluation the automated, user-input independent curve-fitting software ’IFORS’ (Iterative Fitting Of Raman Spectra) has been written. To reduce the bias due to the experimental setup, a reference sample series has been collected that covers a temperature range of 160 °C to 600 °C. Multi-wavelength resonance Raman spectroscopy was performed during sample preparation on dispersed vitrinites that experienced diagenetic to epizonal pressure and temperature conditions to infer the analogy between the RSCM-method and reflectance of dispersed organic matter. The IFORS software allowed to derive the scaled total area (STA) Raman parameter which accurately characterizes Raman spectra of carbonaceous matter. Based on the resonance Raman data it could be shown that STA-RSCM method can be used in analogue to vitrinite reflectance, that this method is robust to sample preparation, especially polishing, and that the resonance Raman spectra of vitrinite reflect a two-stage molecular evolution during coalification and graphitization. During the first stage, which ends approximately after the CM passed through the gas-window, linear polycyclic aromatic structure grow, while the second stage indicates growth of condensed polycyclic aromatic structures. The STA-RSCM method has been extended to describe the Raman spectra of metamorphic CM and was successfully calibrated to the reference sample series. Thus, a revised RSCMgeothermometer valid from 160 °C to 600 °C is proposed. The sample series is available to the public and is supposed to be extended by the scientific community to further increase the quality of the reference series. When used in combination, the STA-RSCM method and the reference sample series will improve the overall comparability among laboratories and will advance the general applicability of this geothermometric method.2018-04-3

Inherited Grain‐Size Distributions: Effect on Heavy‐Mineral Assemblages in Modern and Ancient Sediments

AbstractHeavy‐mineral suites are used widely in sandstone provenance and are key when connecting source and sink. When characterizing provenance related signatures, it is essential to understand the different factors that may influence a particular heavy‐mineral assemblage for example, chemical weathering or diagenetic processes. Hydrodynamics, causing size‐density sorting, exert major control on the distribution of heavy minerals. Here, we highlight the effect of grain‐size inheritance, essentially the absence of certain grain sizes within a specific heavy‐mineral species, on two distinct types of sediments. Modern deposits from a high‐energy beach in NW Denmark give an analog for heavily reworked sediment, primarily controlled by hydrodynamic processes. In contrast, three Palaeogene turbidite successions in the Eastern Alps were sampled, presenting a more complex history that includes diagenesis. All samples were processed for their heavy‐mineral compositions using Raman spectroscopy, and several techniques applied to determine the effect of grain‐size inheritance. Results show that (a) even within the hydrodynamically well‐sorted beach and placer deposits, evidence of grain‐size inheritance is apparent, and (b) turbidites of variable heavy‐mineral composition show strong effects of grain‐size inheritance for several mineral species. Moreover, considerable intersample contrasts within single turbidite beds are observed. We enforce the importance of understanding grain‐size inheritance, as well as other processes effecting size‐density relations in clastic sediment that go well beyond purely hydrodynamic control of intrasample heavy‐mineral variability.Plain Language Summary: Heavy minerals are commonly found within sediments and sedimentary rocks and can tell us from which source regions the sediment may have originated. However, it is important to understand that the type, size, and abundance of particular heavy minerals can change depending on factors such as environmental conditions. The size, shape, and density of the heavy minerals also limits when and where they will settle and/or stay. A lack of big or small grains of a particular heavy mineral in the source rocks dictates the size of the minerals deposited; this is known as grain‐size inheritance. Using both ancient and modern sediment, we are looking for traces of grain‐size inheritance. Surprisingly, in all samples investigated we noted effects of grain‐size inheritance, for different heavy‐mineral types. The modern beach sediments, as expected, show more impact of hydraulic processes, but inherited grain sizes are still apparent. Within the ancient examples, grain‐size inheritance is more obvious, with further variations even observed between samples collected from the same area. Having identified this control on grain size, we can highlight the importance of understanding this effect when analyzing clastic sediments.Key Points: Understanding factors that can modify a heavy‐mineral assemblage is fundamental in provenance analysis Heavy minerals of two distinct sedimentary environments were analyzed and compared to their “ideal” hydrodynamically sorted compositions Several heavy‐mineral species of modern and ancient settings were identified to be influenced by grain‐size inheritance from the source https://doi.org/10.25625/MVUIJ

Semi-Automated Heavy-Mineral Analysis by Raman Spectroscopy

A significant amount of information on sedimentary provenance is encoded in the heavy minerals of a sediment or sedimentary rock. This information is commonly assessed by optically determining the heavy-mineral assemblage, potentially followed by geochemical and/or geochronological analysis of specific heavy minerals. The proposed method of semi-automated heavy-mineral analysis by Raman spectroscopy (Raman-HMA) aims to combine the objective mineral identification capabilities of Raman spectroscopy with high-resolution geochemical techniques applied to single grains. The Raman-HMA method is an efficient and precise tool that significantly improves the comparability of heavy-mineral data with respect to both overall assemblages and individual compositions within solid solution series. Furthermore, the efficiency of subsequent analysis is increased due to identification and spatial referencing of the heavy minerals in the sample slide. The method is tested on modern sediments of the Fulda river (central Germany) draining two Miocene volcanic sources (Vogelsberg, Rhön) resting on top of Lower Triassic siliciclastic sediments. The downstream evolution of the volcanic detritus is documented and the capability to analyze silt-sized grains has revealed an additional eolian source. This capability also poses the possibility of systematically assessing the heavy-mineral assemblages of shales, which are often disregarded in sedimentary provenance studies

Analytical data of rutile and garnet chemistry of sandstone samples from the Enticho Sandstone and the Edaga Arbi Glacials (Palaeozoic, Ethiopia)

We use heavy minerals and rutile and garnet chemical compositions to constrain the provenance of two glaciogenic sandstone formations that build up the Palaeozoic succession in Ethiopia. The heavy mineral assemblage of the Upper Ordovician–Lower Silurian Enticho Sandstone is dominated by ultra-stable minerals, implying high maturity of the sediment. Variable amounts of garnet are present as well. The Carboniferous–Permian Edaga Arbi Glacials contain mainly less stable heavy minerals, such as garnet and apatite, suggesting little chemical alteration. A combination of magmatic and metamorphic source rocks is likely for both formations. Rutile and garnet chemistry point to mainly amphibolite-facies and to a lesser extent granulite-facies metamorphic source rocks with generally slightly higher metamorphic temperatures for detrital heavy minerals in the Enticho Sandstone. We conclude that the Enticho Sandstone is mainly the product of reworked mature Cambrian–Ordovician sediment, which may have been supplied via the Gondwana super-fan system. Locally, glaciers of the Late Ordovician glaciation eroded fresh basement material, delivering the garnet. For the Edaga Arbi Glacials, a rather proximal provenance is likely. The potential source area is the southern hinterland, where Precambrian low-to higher grade metamorphic rocks of the Arabian–Nubian Shield occur at the transition to the Mozambique Belt.Final thirt published dataset from the dissertatio

Estimation of radiation damage in titanites using Raman spectroscopy

International audienceRecent studies have shown that a-damage in titanite influences He diffusivity and thus the closure temperature of the (U-Th)/He system in titanite. We compare different methods for measuring the alpha-dose in titanite by Raman spectroscopy. Raman spectra of randomly oriented titanite fragments from the Archean Karelian domain in eastern Finland along with some well-studied young titanites and U-Pb standard reference materials were analyzed and related to the concentration of alpha-emitting elements (U and Th) that generated damage in the respective grains. Automated curve-fitting was performed by the IFORS software and different curve-fitting protocols were tested and compared.The Raman bands at 424 and 465 cm(-1) show a good correlation of full-width at half maximum (FWHM) and position with the alpha-dose. However, these bands are not always present because titanite is highly anisotropic implying that Raman spectra are sensitive to orientation. The intensity-weighted mean FWHM (iw-FWHM) of all Raman bands of a spectrum proves to be the most robust measure of the alpha-dose. A simplified fitting approach considering 15 peaks is sufficient to describe the accumulated alpha-dose. For alpha-doses below 5 x 10(16)alpha/g the iw-FWHM is independent of alpha-dose and ranges from 25 to 50 cm-1. Above this value the iw-FWHM increases linearly with increasing alpha-dose up to 3 x 10(18)alpha/g. The linear correlation can be described as iw-FWHM[cm(-1)] approximate to 39(+/- 1.2)[cm(-1)] + 3.84(+0.61,-0.26) x 10(-17)[cm(-1)/(alpha/g)] x alpha-dose[alpha/g]. The approach provides a pre-selection method to optimize the range of alpha-doses of titanite crystals to be dated by (U-Th)/He thermochronology

Post-Caledonian brittle deformation in the Bergen area,West Norway: results from K–Ar illite fault gouge dating

Post-Caledonian extension during orogenic collapse and Mesozoic rifting in the West Norway–northern North Sea region was accommodated by the formation and repeated reactivation of ductile shear zones and brittle faults. Offshore, the Late Palaeozoic–Mesozoic rift history is relatively well known; extension occurred mainly during two rift phases in the Permo–Triassic (Phase 1) and Mid–Late Jurassic (Phase 2). Normal faults in the northern North Sea, e.g., on the Horda Platform, in the East Shetland Basin and in the Viking Graben, were initiated or reactivated during both rift phases. Onshore, on the other hand, information on periods of tectonic activity is sparse as faults in crystalline basement rocks are difficult to date. K– Ar dating of illite that grows synkinematically in fine-grained fault rocks (gouge) can greatly help to determine the time of fault activity, and we apply the method to nine faults from the Bergen area. The K–Ar ages are complemented with X-ray diffraction analyses to determine the mineralogy, illite crystallinity and polytype composition of the samples. Based on these new data, four periods of onshore fault activity could be defined: (1) the earliest growth of fault-related illite in the Late Devonian–Early Carboniferous (>340 Ma) marks the waning stages of orogenic collapse; (2) widespread latest Carboniferous–Mid Permian (305–270 Ma) fault activity is interpreted as the onset of Phase 1 rifting, contemporaneous with rift-related volcanism in the central North Sea and Oslo Rift; (3) a Late Triassic–Early Jurassic (215–180 Ma) period of onshore fault activity postdates Phase 1 rifting and predates Phase 2 rifting and is currently poorly documented in offshore areas; and (4) Early Cretaceous (120–110 Ma) fault reactivation can be linked either to late Phase 2 North Sea rifting or to North Atlantic rifting