Effects of biodegradation on diamondoid distribution in crude oils from the Bongor Basin,Chad

The sensitivity of biodegradation on diamondoids was investigated using a series of biodegraded oil samples from the Ronier tectonic unit of Bongor Basin,Chad.The results suggest that diamondoids,including adamantanes(As)and diamantanes(Ds),are relatively resistant to biodegradation and obvious biodegradation was observed in oils with a Peters-Moldowan(PM)biodegradation rank of 6 or more.Overall,the sensibility of biodegradation on diamondoids is generally similar to hopanes and regular steranes.As biodegradation evolves,the changes in concentration and components of diamondoids show that the biodegradation process is selective and stepwise.The significant increase of MD/MA and DMD/DMA for oils with a PM ranking 6^(+) indicates that diamantanes are generally more resistant to biodegradation than adamantanes.The similar trends of DMA/MA,EA/MA,MD/D,DMD/MD and other relevant indexes,show that higher alkylation homologs are more resistant to biodegradation.The commonly used diamondoid ratios,such as MAI,EAI,MDI and DMID-1,are obviously affected by biodegradation at the stage of high-level biodegradation,which may indicate that these ratios should be used with caution in case of severely degraded oils.

The effect of volatile components in oil on evolutionary character- istics of diamondoids during oil thermal pyrolysis

On the basis of the results of simulation experiments, now we better understand the contribution of high carbon number hydrocarbons to diamondoid generation during thermal pyrolysis of crude oil and its sub-fractions(saturated, aromatic, resin, and asphalene fractions). However, little is known about the effect of volatile components in oil on diamondoid generation and diamondoid indices due to the lack of attention to these components in experiments. In this study, the effect of volatile components in oil on diamondoid generation and maturity indices was investigated by the pyrolysis simulation experiments on a normal crude oil from the HD23 well of the Tarim Basin and its residual oil after artificial volatilization, combined with quantitative analysis of diamondoids. The results indicate that the volatile components(≤n C12) in oil have an obvious contribution to the generation of adamantanes, which occurs mainly in the early stage of oil cracking(Easy Ro<1.0%), and influences the variations in maturity indices of adamantanes; but they have no obvious effect on the generation and maturity indices of diamantanes. Therefore, some secondary alterations e.g., migration, gas washing, and biodegradation, which may result in the loss of light hydrocarbons in oil under actual geological conditions, could affect the identification of adamantanes generated during the late-stage cracking of crude oil, and further influence the practical application of adamantane indices.

Detection and significance of higher thiadiamondoids and diamondoidthiols in oil from the Zhongshen 1C well of the Tarim Basin, NW China

Oil and gas breakthroughs have been achieved in the Zhongshen 1(ZS1) and 1 C(ZS1 C) wells in Cambrian pre-salt from the Tarim Basin in northwest China. However, Middle and Lower Cambrian reservoirs reveal substantial differences in the geochemistry and secondary alteration characteristics between the oils collected from the two wells. High concentrations of thiadiamondoids and diamondoidthiols, including thiatetramantanes, tetramantanethiols, thiapentamantanes, and pentamantanethiols, are detected in the organic sulfur compound fraction of concentrated oil collected from the ZS1 C well, which samples the Lower Cambrian Xiaoerbulake Formation. Higher diamondoids, such as tetramantanes, pentamantanes, hexamantanes, and cyclohexamantane, also occur in the saturate fractions of the concentrated ZS1 C oil. The presence of these compounds is verified by mass spectra analysis and comparison with previous studies. During thermochemical sulfate reduction(TSR), the cage of higher diamondoids is interpreted to open because of sulfur radicals forming open-cage higher diamondoid-like thiols, followed by cyclization that leads to the formation of high thiadiamondoids. Using D_(16)-adamantane as an internal standard, the concentrations of lower diamondoids and thiadiamondoids of non-concentrated Cambrian oil from well ZS1 C are 83874 and8578 μg/g, respectively, which are far higher than Cambrian oil from well ZS1 and most Ordovician oils in the Tarim Basin. The high concentrations of lower thiadiamondoids and occurrence of higher thiadiamondoids and diamondoidthiols support that the oil from well ZS1 C is a product of severe TSR alteration.

Crude oil cracking in deep reservoirs:A review of the controlling factors and estimation methods

The natural cracking of crude oils in deep reservoirs has gained great interest due to continuously increasing depth of petroleum exploration and exploitation.Complex oil compositions and surroundings as well as complicated geological evolutions make oil cracking in nature much more complex than industrial pyrolysis.So far,numerous studies,focused on this topic,have made considerable progress although there still exist some drawbacks.However,a comprehensive review on crude oil cracking is yet to be conducted.This article systematically reviews the controlling factors of oil cracking from six aspects,namely,oil compositions,temperature and time,pressure,water,minerals and solid organic matter.We compare previous experimental and modelling results and present new field cases.In the following,we evaluate the prevailing estimation methods for the extent of oil cracking,and elucidate other factors that may interfere with the application of these estimation methods.This review will be helpful for further investigations of crude oil cracking and provides a guide for estimation of the cracking extent of crude oils.

An examination by GC×GC-TOFMS of organic molecules present inhighly degraded oils emerging from Caribbean terrestrial seeps of Cretaceous age

For our ancestors, oil seeps were both a fascination and a resource but as the planet's reserves of high quality low density oil becomes increasingly depleted, so there is now a renewed interest in heavier,biodegraded oils such as those encountered in terrestrial seeps. One such seep is Pitch Lake in the Caribbean island of Trinidad, which is the largest natural deposit of asphalt in the world. At the northern end of the Caribbean, oil emerges along a tectonic contact on the island on Cuba. The sources of the oils from these seeps are relatively recent and both are subject to intense weathering due to the tropical conditions. When analysed by gas chromatography(GC) both oils appear as unresolved complex mixtures(UCM) and show a very high degree of biodegradation thus presenting an analytical challenge. In this case study, these two Caribbean seep oils were analysed by comprehensive two dimensional GC with time of flight mass spectrometry(GC×GC-TOFMS) to expose many thousands of the individual compounds that comprise the UCM. The high chromatographic resolution of the GC×GC-TOFMS produced good quality mass spectra allowing many compounds including molecular fossil ‘biomarkers' to be identified. Compound classes included diamondoid hydrocarbons, demethylated hopanes and secohopanes, mono-and tri-aromatic steroids. D-ring aromatised structures of the 8,14-seco-hopanes,including demethylated forms were present in both oils but further demethylation, probably at position C-25 during biodegradation, was only observed in the Pitch Lake oil. Many polycyclic aromatic hydrocarbons(PAHs) were absent although the fungal-derived pentacyclic PAH perylene was present in both oils. The presence of the angiosperm biomarker lupane in the Pitch Lake oil constrained the age to the Late Cretaceous. The higher degree of biodegradation observed in the Cuban oil was likely due to relatively slow anaerobic processes whereas oil within Pitch Lake was probably subject to additional more rapid aerobic metabolism within the lake.

Nanodiamonds with powerful ability for drug delivery and biomedical applications:Recent updates on in vivo study and patents

Nanodiamonds are novel nanosized carbon building blocks possessing varied fascinating mechanical,chemical,optical and biological properties,making them significant active moiety carriers for biomedical application.These are known as the most‘captivating’crystals attributed to their chemical inertness and unique properties posing them useful for variety of applications in biomedical era.Alongside,it becomes increasingly important to find,ascertain and circumvent the negative aspects associated with nanodiamonds.Surface modification or functionalization with biological molecules plays a significant role in managing the toxic behavior since nanodiamonds have tailorable surface chemistry.To take advantage of nanodiamond potential in drug delivery,focus has to be laid on its purity,surface chemistry and other considerations which may directly or indirectly affect drug adsorption on nanodiamond and drug release in biological environment.This review emphasizes on the basic properties,synthesis techniques,surface modification techniques,toxicity issues and biomedical applications of nanodiamonds.For the development of nanodiamonds as an effective dosage form,researchers are still engaged in the in-depth study of nanodiamonds and their effect on life interfaces.

Heavy-organic particle deposition from petroleum fluid flow in oil wells and pipelines

Suspended asphaltenic heavy organic particles in petroleum fluids may stick to the inner walls of oil wells and pipelines. This is the major reason for fouling and arterial blockage in the petroleum industry. This report is devoted the study of the mechanism of migration of suspended heavy organic particles towards the walls in oil-producing wells and pipelines. In this report we present a detailed analytical model for the heavy organics suspended particle deposition coefficient corresponding to petroleum fluids flow production conditions in oil wells. We predict the rate of particle deposition during various turbulent flow regimes. The turbulent boundary layer theory and the concepts of mass transfer are utilized to model and calculate the particle deposition rates on the walls of flowing conduits. The developed model accounts for the eddy diffusivity, and Brownian diffusivity as well as for inertial effects. The analysis presented in this paper shows that rates of particle deposition （during petroleum fluid production） on the walls of the flowing channel due solely to diffusion effects are small. It is also shown that deposition rates decrease with increasing particle size. However, when the process is momentum controlled （large particle sizes） higher deposition rates are expected.

Re-Examination of the Oil and Gas Origins in the Kekeya Gas Condensate Field,Northwest China——A Case Study of Hydrocarbon-Source Correlation Using Sophisticated Geochemical Methods

This work discussed the origins, alteration and accumulation processes of the oil and gas in the Kekeya gas condensate field based on molecular compositions, stable carbon isotopes, light hydrocarbons, diamondoid hydrocarbons and biomarker fingerprints. A comparison study is also made between the geochemical characteristics of the Kekeya hydrocarbons and typical marine and terrigenous hydrocarbons of the Tarim Basin. Natural gas from the Kekeya gas condensate field is derived from Middle–Lower Jurassic coal measures while the condensates are derived from Carboniferous–Permian marine source rocks with a higher maturity. In the study area, both natural gas and condensates have experienced severe water washing. A large amount of methane was dissolved into the water, resulting in a decrease in the dryness coefficient. Water washing also makes the carbon isotopic compositions of the natural gas more negative and partially reverse. Considering that the gas maturities are higher than once expected, gas generation intensity in the study area should be much stronger and the gas related to the Jurassic coal measures could promise a greater prospecting potential. As a result of evaporative fractionation, the Kekeya condensates are enriched in saturates and lack aromatics. Evaporative fractionation disguises the original terrigenous characteristics of the light hydrocarbons associated with the natural gas, making it appear marinesourced. Thus, alteration processes should be fully taken into consideration when gas–source correlations are carried out based on light hydrocarbons. With the condensates discovered in the study area all being ＂migration phase＂, the pre-salt Cretaceous and Jurassic reservoirs may promise great exploration potential for the ＂residual phase＂ hydrocarbons. This research not only is of significance for oil and gas exploration in the southwest Tarim Basin, but also sheds light on the oil/gas-source correlations in general.

Analyzing crude oils from the Junggar Basin(NW China) using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry(GC×GC-TOFMS)

As a new technology of analyzing crude oils, comprehensive two-dimensional gas chromatography cou- pled with time-of-flight mass spectrometry （GCxGC- TOFMS） has received much research attention. Here we present a case study in the Junggar Basin of NW China. Results show that the hydrocarbons, including saturates and aromatics, were all well-separated without large co- elution, which cannot be realized by conventional one-dimensional GC-MS. The GC×GC technique is especially effective for analyzing aromatics and low-to-middle- molecular-weight hydrocarbons, such as diamondoids. The geochemical characteristics of crude oils in the study area were investigated through geochemical parameters extracted by GC×GC-TOFMS, improving upon the understanding obtained by GC-MS. Thus, the work here represents a new successful application of GC×GC- TOFMS, showing its broad usefulness in petroleum geochemistry.

Two Interpenetrated Dia-type Coordination Polymers Constructed from Mixed Dicarboxylate and Bis(imidazol)-based Ligands

Two novel interpenetrating diamond frameworks, namely [Cd（mal）（bix）]n （1）and {[Zn（sub）（bib）]n.H2O}. （2）（H2mal = maleic acid, H2sub = suberic acid, bix = 1,4-bis（imidazol- l-ylmethyl）-benzene, bib = 1,4-bis（N-imidazolyl）butane） were hydrothermally synthesized and characterized by elemental analysis, infrared spectra （IR）, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the orthorhombic system with space group Pnma and features a 3-fold interpenetrating diamond framework. Compound 2 exhibits a 4-fold interpenetrating diamond network. The luminescent properties of these two compounds have also been investigated in detail.

Lattice dynamics and thermoelectric properties of diamondoid materials

The diamondoid compounds are a large family of important semiconductors,which possess various unique transport properties and had been widely investigated in the fields of photoelectricity and nonlinear optics.For a significantly long period of time,diamondoid materials were not given much attention in the field of thermoelectricity.However,this changed when a series of diamondoid compounds showed a thermoelectric figure of merit(ZT)greater than 1.0.This discovery sparked considerable interest in further exploring the thermoelectric properties of diamondoid materials.This review aims to provide a comprehensive view of our current understanding of thermal and electronic transport in diamondoid materials and stimulate their development in thermoelectric applications.We present a collection of recent discoveries concerning the lattice dynamics and electronic structure of diamondoid materials.We review the underlying physics responsible for their unique electrical and phonon transport behaviors.Moreover,we provide insights into the advancements made in the field of thermoelectricity for diamondoid materials and the corresponding strategies employed to optimize their performance.Lastly,we emphasize the challenges that lie ahead and outline potential avenues for future research in the domain of diamondoid thermoelectric materials.