Proto-solid bitumen in petroleum altered by thermochemical sulfate reduction

Thermochemical sulfate reduction (TSR) involves a complex series of redox reactions whereby petroleum is oxidized by sulfate forming H₂S and CO_2. A highly aromatic, sulfur rich carbonaceous residue, which we define as TSR-solid bitumen, is commonly seen in reservoir rocks where TSR has occurred. Using atmospheric pressure photoionization (APPI) Fourier transform ion cyclotron resonance (FTICR) mass spectrometry, we find that TSR altered oils and condensates contain highly condensed polynuclear aromatic and naphthenoaromatic species with 0–3 S atoms. These chemical species are not present in petroleum fluids of equivalent maturity that have not experienced TSR and must have been formed by the TSR process. We call these species proto-solid bitumen as they represent the type of organic compounds that could easily precipitate from the TSR altered oils with slight chemical alteration or changes in reservoir conditions.     

Regional operational and environmental performance evaluation in China: non-radial DEA methodology under natural and managerial disposability

In this article, we used a non-radial DEA under natural and managerial disposability to measure the unified efficiency of 30 administrative regions in China and then evaluated their operational and environmental performances. We proposed the performance progress unified index (PPUI) based on the non-radial DEA methodology in a time horizon under natural and managerial disposability with a crossover to measure the performance variety of DMUs. The results of the unified efficiency measured under natural and managerial disposability showed that both operational and environmental performance in eastern China were the highest among the three regions during 2000–2011. The PPUIs under natural and managerial disposability indicated that the operational and environmental performance of the three regions improved during 2000–2011, and the rate of operational and environmental performance of eastern China was higher than the other two regions.

     

Regional operational and environmental performance evaluation in China: non-radial DEA methodology under natural and managerial disposability

In this article, we used a non-radial DEA under natural and managerial disposability to measure the unified efficiency of 30 administrative regions in China and then evaluated their operational and environmental performances. We proposed the performance progress unified index (PPUI) based on the non-radial DEA methodology in a time horizon under natural and managerial disposability with a crossover to measure the performance variety of DMUs. The results of the unified efficiency measured under natural and managerial disposability showed that both operational and environmental performance in eastern China were the highest among the three regions during 2000–2011. The PPUIs under natural and managerial disposability indicated that the operational and environmental performance of the three regions improved during 2000–2011, and the rate of operational and environmental performance of eastern China was higher than the other two regions.     

Natural occurrence of higher thiadiamondoids and diamondoidthiols in a deep petroleum reservoir in the Mobile Bay gas field

A series of higher thiadiamondoids and diamondoidthiols, including thiatetramantanes, tetramantanethiols, thiapentamantanes, pentamantanethiols, thiahexamantanes, hexamantanethiols and thiacylcohexamantane, was discovered in a gas condensate produced from a very deep (6274 m, 20,585 ft) petroleum reservoir in the Bon Secour Bay in the Mobile Bay gas field, located offshore Alabama in the northern Gulf of Mexico, USA. This appears to be the first reported natural occurrence of these compounds. Several isomers of higher thiadiamondoids and diamondoidthiols were identified using full scan gas chromatography-mass spectrometry (GC-MS) coupled with GC-sulfur chemiluminescence detection (GC-SCD) and GC × GC-time of flight mass spectrometry (GC × GC-TOFMS). These higher thiadiamondoids and diamondoidthiols are associated with abundant lower homologs including thiaadamantanes, thiadiamantanes, thiatriamantanes and their thiol groups. The origin of these compounds in petroleum has not been reported. It is speculated that similar to lower thiadiamondoids and diamondoidthiols, higher ones are possibly formed from the sulfurization of their precursor diamondoids during TSR, a conclusion supported by the occurrence of open-cage higher diamondoidthiols and sulfur isotopic data of higher thiadiamondoids and diamondoidthiols isolated from the Mobile Bay condensate. The presence of higher thiadiamondoids and diamondoidthiols is indicative of the occurrence of TSR and can be used to predict sour gas production.