Diamondoids and thiadiamondoids generated from hydrothermal pyrolysis of crude oil and TSR experiments

Diamondoid compounds are widely used to reflect thermal maturation of high mature source rocks or oils and oil cracking extents. However, diamondoids and thiadiamondoids were demonstrated to have newly been generated and decomposed in our hydrothermal pyrolysis of crude oil and TSR experiments. Our results show that adamantanes and diamantanes are generated primarily within the maturity range 0.48–2.1% and 1.2–3.0% EasyRo, respectively. Their formation is enhanced and the decomposition of diamantanes obviously lags at elevated temperatures compared with anhydrous experiments. MDI, EAI, DMAI-1, DMDI-2 may serve as reliable maturity proxies at > ca.1.0% EasyRo, and other isomerization indices (TMAI-1, TMAI-2 and DMAI-2) are effective for the highly mature organic matter at EasyRo > 2.0%. The extent of oil cracking (EOC) calculated from the broadly used (3- + 4-) MD method (Dahl et al. in Nature 399:54–56, 1999) is proven to overestimate, especially for highly cracked samples due to the new generation of (3- + 4-) MD. Still, it can be corrected using a new formula at < 3.0% EasyRo. Other diamondoid-related indices (e.g., EAI, DMDI-2, As/Ds, MAs/MDs, DMAs/DMDs, and DMAs/MDs) can also be used to estimate EOC. However, these indices cannot be applied to TSR-altered petroleum. TSR is experimentally confirmed to generate diamantanes and thiaadmantanes at 1.81% EasyRo likely via direct reactions of reduced S species with hydrocarbons and accelerate the decomposition of diamantanes at > 2.62% EasyRo compared with thermal chemical alteration (TCA). More studies are needed to assess specific mechanisms for the formation of thiadiamondoids under natural conditions.

Taphonomic and Diagenetic Pathways to Protein Preservation, Part I: The Case of Tyrannosaurus rex Specimen MOR 1125

Many recent reports have demonstrated remarkable preservation of proteins in fossil bones dating back to the Permian. However, preservation mechanisms that foster the long-term stability of biomolecules and the taphonomic circumstances facilitating them remain largely unexplored. To address this, we examined the taphonomic and geochemical history of Tyrannosaurus rex specimen Museum of the Rockies (MOR) 1125, whose right femur and tibiae were previously shown to retain still-soft tissues and endogenous proteins. By combining taphonomic insights with trace element compositional data, we reconstruct the postmortem history of this famous specimen. Our data show that following prolonged, subaqueous decay in an estuarine channel, MOR 1125 was buried in a coarse sandstone wherein its bones fossilized while interacting with oxic and potentially brackish early-diagenetic groundwaters. Once its bones became stable fossils, they experienced minimal further chemical alteration. Comparisons with other recent studies reveal that oxidizing early-diagenetic microenvironments and diagenetic circumstances which restrict exposure to percolating pore fluids elevate biomolecular preservation potential by promoting molecular condensation reactions and hindering chemical alteration, respectively. Avoiding protracted interactions with late-diagenetic pore fluids is also likely crucial. Similar studies must be conducted on fossil bones preserved under diverse paleoenvironmental and diagenetic contexts to fully elucidate molecular preservation pathways.

Diamondoids and Thiadiamondoids Generated From Hydrothermal Pyrolysis of Crude Oil and TSR Experiments

Diamondoid compounds are widely used to reflect thermal maturation of high mature source rocks or oils and oil cracking extents. However, diamondoids and thiadiamondoids were demonstrated to have newly been generated and decomposed in our hydrothermal pyrolysis of crude oil and TSR experiments. Our results show that adamantanes and diamantanes are generated primarily within the maturity range 0.48–2.1% and 1.2–3.0% EasyRo, respectively. Their formation is enhanced and the decomposition of diamantanes obviously lags behind at elevated temperatures compared with anhydrous experiments. MDI, EAI, DMAI-1, DMDI-2 may serve as reliable maturity proxies at > ca.1.0% EasyRo, and other isomerization indices (TMAI-1, TMAI-2 and DMAI-2) are effective for the highly mature organic matter at EasyRo > 2.0%. The extent of oil cracking (EOC) calculated from the broadly used 3-+4-MD method (Dahl et al., 1999) is proven to overestimate, especially for highly cracked samples due to the new generation of 3-+4-MD. Still, it can be corrected using a new formula at <3.0% EasyRo. Other diamondoid-related indices (e.g. EAI, DMDI-2, As/Ds, MAs/MDs, DMAs/DMDs, and DMAs/MDs) can also be used to estimate EOC. However, these indices cannot be applied to TSR-altered petroleum. TSR is experimentally confirmed to generate diamantanes and thiaadmantanes at 1.81% EasyRo via direct reactions of reduced S species with hydrocarbons and accelerate the decomposition of diamantanes at > 3.0% EasyRo compared with thermal chemical alteration (TCA).

The Archaeometallurgical Evaluation of Three Bronze Socketed Axes, Discovered in Eastern Romania

This paper presents the study of three bronze socketed axes discovered in Neamţ County, Romania. The surface structures and those from the interface of the corrosion layer with the metal core of the basic alloy were analyzed, in order to elucidate the nature of the materials used and the manufacturing processes. The analyzes by optical microscopy (OM) and electron microscopy (SEM), coupled with X-ray spectrometry (EDX), revealed the type of their degradation during the depositional period, as a result of the processes of chemical alteration and physical damage. A series of metallurgical techniques used were also established, as well as the identification of some finishing and decoration processes that led to the establishment of the objects’ functionality.

Long-Term Aging of Chernobyl Fuel Debris: Corium and “Lava”

Samples of Chernobyl fuel debris, including massive corium and “lava” were collected inside the Chernobyl “Sarcophagus” or “Shelter” in 1990, transported to Leningrad (St. Petersburg) and stored under laboratory conditions for many years. In 2011 aged samples were visually re-examined and it was confirmed that most of them remained intact, although some evidence of self-destruction and chemical alteration were clearly observed. Selected samples of corium and “lava” were affected by static leaching at temperatures of 25, 90 and 150 °C in distilled water. A normalized Pu mass loss (NLPu) from corium samples after 140 days was noted to be 0.5 g/m2 at 25 °C and 1.1 g/m2 at 90 °C. For “lava” samples NLPu was 2.2–2.3 g/m2 at 90 °C for 140 days. The formation of secondary uranyl phases on the surface of corium and “lava” samples altered at 150 °C was confirmed. The results obtained are considered as an important basis for the simulation of fuel debris aging at Fukushima Daiichi nuclear power plant (NPP).