Unraveling the Molecular Structures of Asphaltenes by Atomic Force Microscopy.

Petroleum is one of the most precious and complex molecular mixtures existing. Because of its chemical complexity, the solid component of crude oil, the asphaltenes, poses an exceptional challenge for structure analysis, with tremendous economic relevance. Here, we combine atomic-resolution imaging using atomic force microscopy and molecular orbital imaging using scanning tunnelling microscopy to study more than 100 asphaltene molecules. The complexity and range of asphaltene polycyclic aromatic hydrocarbons are established in detail. Identifying molecular structures provides a foundation to understand all aspects of petroleum science from colloidal structure and interfacial interactions to petroleum thermodynamics, enabling a first-principles approach to optimize resource utilization. Particularly, the findings contribute to a long-standing debate about asphaltene molecular architecture. Our technique constitutes a paradigm shift for the analysis of complex molecular mixtures, with possible applications in molecular electronics, organic light emitting diodes, and photovoltaic devices.

Downhole fluid analysis and asphaltene science for petroleum reservoir evaluation.

Petroleum reservoirs are enshrouded in mysteries associated with all manner of geologic and fluid complexities that Mother Nature can inspire. Efficient exploitation of petroleum reservoirs mandates elucidation of these complexities; downhole fluid analysis (DFA) has proven to be indispensable for understanding both fluids and reservoir architecture. Crude oil consists of dissolved gases, liquids, and dissolved solids, known as the asphaltenes. These different fluid components exhibit fluid gradients vertically and laterally, which are best revealed by DFA, with its excellent precision and accuracy. Compositional gradient analysis falls within the purview of thermodynamics. Gas-liquid equilibria can be treated with a cubic equation of state (EoS), such as the Peng-Robinson EoS, a modified van der Waals EoS. In contrast, the first EoS for asphaltene gradients, the Flory-Huggins-Zuo (FHZ) EoS, was developed only recently. The resolution of the asphaltene molecular and nanocolloidal species in crude oil, which is codified in the Yen-Mullins model of asphaltenes, enabled the development of this EoS. The combination of DFA characterization of gradients of reservoir crude oil with the cubic EoS and FHZ EoS analyses brings into view wide-ranging reservoir concerns, such as reservoir connectivity, fault-block migration, heavy oil gradients, tar mat formation, huge disequilibrium fluid gradients, and even stochastic variations of reservoir fluids. New petroleum science and DFA technology are helping to offset the increasing costs and technical difficulties of exploiting ever-more-remote petroleum reservoirs.

Minimization of fragmentation and aggregation by laser desorption laser ionization mass spectrometry.

Measuring average quantities in complex mixtures can be challenging for mass spectrometry, as it requires ionization and detection with nearly equivalent cross-section for all components, minimal matrix effect, and suppressed signal from fragments and aggregates. Fragments and aggregates are particularly troublesome for complex mixtures, where they can be incorrectly assigned as parent ions. Here we study fragmentation and aggregation in six aromatic model compounds as well as petroleum asphaltenes (a naturally occurring complex mixture) using two laser-based ionization techniques: surface assisted laser desorption ionization (SALDI), in which a single laser desorbs and ionizes solid analytes; and laser ionization laser desorption mass spectrometry (L(2)MS), in which desorption and ionization are separated spatially and temporally with independent lasers. Model compounds studied include molecules commonly used as matrices in single laser ionization techniques such as matrix assisted laser desorption ionization (MALDI). We find significant fragmentation and aggregation in SALDI, such that individual fragment and aggregate peaks are typically more intense than the parent peak. These fragment and aggregate peaks are expected in MALDI experiments employing these compounds as matrices. On the other hand, we observe no aggregation and only minimal fragmentation in L(2)MS. These results highlight some advantages of L(2)MS for analysis of complex mixtures such as asphaltenes.

The asphaltenes.

Asphaltenes, the most aromatic of the heaviest components of crude oil, are critical to all aspects of petroleum utilization, including reservoir characterization, production, transportation, refining, upgrading, paving, and coating materials. The asphaltenes, which are solid, have or impart crucial and often deleterious attributes in fluids such as high viscosity, emulsion stability, low distillate yields, and inopportune phase separation. Nevertheless, fundamental uncertainties had precluded a first-principles approach to asphaltenes until now. Recently, asphaltene science has undergone a renaissance; many basic molecular and nanocolloidal properties have been resolved and codified in the modified Yen model (also known as the Yen-Mullins model), thereby enabling predictive asphaltene science. Advances in analytical chemistry, especially mass spectrometry, enable the identification of tens of thousands of distinct chemical species in crude oils and asphaltenes. These and other powerful advances in asphaltene science fall under the banner of petroleomics, which incorporates predictive petroleum science and provides a framework for future developments.

Molecular orientation of asphaltenes and PAH model compounds in Langmuir-Blodgett films using sum frequency generation spectroscopy.

Asphaltenes are an important class of compounds in crude oil whose surface activity is important for establishing reservoir rock wettability which impacts reservoir drainage. While many phenomenological interfacial studies with crude oils and asphaltenes have been reported, there is very little known about the molecular level interactions between asphaltenes and mineral surfaces. In this study, we analyze Langmuir-Blodgett films of asphaltenes and related model compounds with sum frequency generation (SFG) vibrational spectroscopy. In SFG, the polarization of the input (vis, IR) and output (SFG) beams can be varied, which allows the orientation of different functional groups at the interface to be determined. SFG clearly indicates that asphaltene polycyclic aromatic hydrocarbons (PAHs) are highly oriented in the plane of the interface and that the peripheral alkanes are transverse to the interface. In contrast, model compounds with oxygen functionality have PAHs oriented transverse to the interface. Computational quantum chemistry is used to support corresponding band assignments, enabling robust determination of functional group orientations.

Analysis of petroleum compositional similarity using multiway principal components analysis (MPCA) with comprehensive two-dimensional gas chromatographic data.

The accurate establishment of oil similarity is a longstanding problem in petroleum geochemistry and a necessary component for resolving the architecture of an oil reservoir. Past limitations have included the excessive reliance on a relatively small number of biomarkers to characterize such complex fluids as crude oils. Here we use multiway principal components analysis (MPCA) on large numbers of specific chemical components resolved with comprehensive two-dimensional gas chromatography-flame ionization detection (GC×GC-FID) to determine the molecular relatedness of eight different maltene fractions of crude oils. MPCA works such that every compound eluting within the same first and second dimension retention time is quantitatively compared with what elutes at that same retention times within the other maltene fractions. Each maltene fraction and corresponding MPCA analysis contains upwards of 3500 quantified components. Reservoir analysis included crude oil sample pairs from around the world that were collected sequentially at depth within a single well, collected from multiple depths in the same well, and from different depths and different wells but thought to be intersected by the same permeable strata. Furthermore, three different regions of each GC×GC-FID chromatograms were analysed to evaluate the effectiveness of MPCA to resolve compositional changes related to the source of the oil generating sediments and its exposure to biological and/or physical weathering processes. Compositional and instrumental artefacts introduced during sampling and processing were also quantitatively evaluated. We demonstrate that MPCA can resolve multi-molecular differences between oil samples as well as provide insight into the overall molecular relatedness between various crude oils.

Surface chemistry and spectroscopy of UG8 asphaltene Langmuir film, part 2.

While there has been much focus on asphaltenes in toluene, there has been much less focus on asphaltenes in other solvents. It is important to quantify characteristics of asphaltenes in solvents besides toluene in order to better assess their molecular architecture as well as their fundamental aggregation characteristics. The present work focuses on the investigation of UG8 asphaltene Langmuir films at the air-water interface using chloroform as spreading solvent. The results are compared to the results recently obtained using toluene as spreading solvent. Surface pressure-area isotherms and UV-vis spectroscopy indicate that asphaltenes form smaller nanoaggregates in chloroform than in toluene in similar concentration ranges. Still these nanoaggreates share common features with those in toluene. From the surface pressure-area and compression-decompression isotherms, Brewster angle microscopy, and p-polarized infrared reflection-absorption spectroscopy, it was concluded that small size aggregates are spread on the water surface and the compression of the film leads to formation of large aggregates. The films (Langmuir-Schaefer and Langmuir-Blodgett) studied by atomic force microscopy reveal the existence of nanoaggregates spread on the water surface that coexist with large aggregates formed during compression. In addition to these findings, the spreading solvent, chloroform, allows the determination of asphaltene absorption bands using in situ UV-vis spectroscopy at the air-water interface after 15 min waiting time period. The absorbance data carried out after waiting a time period of 1 h shows similar features with the ones carried out after only 15 min; therefore, there is no need to wait 1 h as in the case when toluene is used as spreading solvent. A comparison of the data obtained from chloroform and toluene shows that smaller aggregate sizes are obtained from chloroform as suggested from the surface pressure-area isotherm, in situ UV-vis spectroscopy, and atomic force microscopy. Nevertheless, the similarity of these nanoaggregates in different solvents suggests this formation is a fundamental property of asphaltenes. Moreover, the lack of the isolated absorption band for one-ring aromatics and only a small peak for two-ring aromatics in the UV spectrum of asphaltenes indicate that these groups are not present in asphaltenes in significant quantities.

Surface chemistry and spectroscopy of UG8 asphaltene Langmuir film, part 1.

This research focuses on a systematic investigation of UG8 asphaltene Langmuir films at the air-water interface using toluene as the spreading solvent. From the surface pressure-area isotherms, it was concluded that small-sized aggregates are spread on the water surface and the compression of the film leads to formation of large aggregates. Our methods provide a stringent test and confirmation for the formation of corresponding asphaltene nanoaggregates that have recently been proposed for bulk solutions. These results were confirmed by compression-decompression isotherms, Brewster angle microscopy, and p-polarized infrared reflection-absorption spectroscopy. The transfer of a single layer using both the Langmuir-Schaefer and Langmuir-Blodgett deposition techniques shows different aggregate shapes depending on the technique used as imaged using atomic force microscopy. The films reveal the existence of nanoaggregates spread on the water surface that coexist with large aggregates formed during compression. For the nanoaggregate, the thickness of the Langmuir-Schaefer and Langmuir-Blodgett films determined by AFM is consistent with small aggregation numbers of nanoaggregates determined by Langmuir film compression. In addition to these findings, the spreading solvent, toluene, was found to be trapped within the aggregates as confirmed by in situ UV-vis spectroscopy at the air-water interface. This result was possible only after waiting a time period of 1 h to allow the complete evaporation of the spreading solvent. This is the only study that reveals the presence of the in situ toluene within the UG8 aggregates directly at the air-water interface.

Two-step laser mass spectrometry of asphaltenes.

Defined by their solubility in toluene and insolubility in n-heptane, asphaltenes are a highly aromatic, polydisperse mixture consisting of the heaviest and most polar fraction of crude oil. Although asphaltenes are critically important to the exploitation of conventional oil and are poised to rise in significance along with the exploitation of heavy oil, even as fundamental a quantity as their molecular weight distribution is unknown to within an order of magnitude. Laser desorption/ionization (LDI) mass spectra vary greatly with experimental parameters so are difficult to interpret: some groups favor high laser pulse energy measurements (yielding heavy molecular weights), arguing that high pulse energy is required to detect the heaviest components of this mixture; other groups favor low pulse energy measurements (yielding light molecular weights), arguing that low pulse energy is required to avoid aggregation in the plasma plume. Here we report asphaltene mass spectra recorded with two-step laser mass spectrometry (L2MS), in which desorption and ionization are decoupled and no plasma is produced. L2MS mass spectra of asphaltenes are insensitive to laser pulse energy and other parameters, demonstrating that the asphaltene molecular weight distribution can be measured without limitation from insufficient laser pulse energy or plasma-phase aggregation. These data resolve the controversy from LDI, showing that the asphaltene molecular weight distribution peaks near 600 Da and previous measurements reporting much heavier species suffered from aggregation effects.

Identification and quantification of alkene-based drilling fluids in crude oils by comprehensive two-dimensional gas chromatography with flame ionization detection.

Comprehensive two-dimensional gas chromatography with flame ionization detection (GC x GC-FID) was used to measure alkene-based drilling fluids in crude oils. Compared to one-dimensional gas chromatography, GC x GC-FID is more robust for detecting alkenes due to the increased resolution afforded by second dimension separations. Using GC x GC-FID to analyze four oil samples from one reservoir contaminated with the same drilling fluid, C(15), C(16), C(17), C(18) and C(20) alkenes were identified. The drilling fluid that contaminated these samples also differed from another commercially obtained fluid, which only contained C(16) and C(18) alkenes. These results should motivate the petroleum industry to consider GC x GC-FID for measuring drilling fluids.

Uncertainty analysis of visible and near-infrared data of hydrocarbons.

Measurement of physical and chemical properties of hydrocarbons plays an important role in the exploration and production of oil wells. In situ measurement of chemical properties of hydrocarbons makes use of visible and near-infrared (vis-NIR) absorption spectra of hydrocarbons. Uncertainty analysis of these fluid properties is central to developing a fundamental understanding of the distribution of hydrocarbons in the reservoir. In this manuscript, we describe an algorithm called the fluid comparison algorithm (FCA), which provides a statistical framework to quantify and compare hydrocarbon fluid properties and associated uncertainties derived from vis-NIR measurements. The inputs to FCA are the magnitude and uncertainty of vis-NIR spectroscopy data of two hydrocarbons. The output of FCA is a probability that two fluids are statistically different. FCA lays the foundations for subsequent optimization and capture of representative reservoir hydrocarbons. Furthermore, in some circumstances, it can also enable real-time decisions to identify reservoir compartmentalization and hydrocarbon composition gradients in natural oil reservoirs.

Diffusivity of asphaltene molecules by fluorescence correlation spectroscopy.

Using fluorescence correlation spectroscopy (FCS) we measure the translational diffusion coefficient of asphaltene molecules in toluene at extremely low concentrations (0.03-3.0 mg/L): where aggregation does not occur. We find that the translational diffusion coefficient of asphaltene molecules in toluene is about 0.35 x 10(-5) cm(2)/s at room temperature. This diffusion coefficient corresponds to a hydrodynamic radius of approximately 1 nm. These data confirm previously estimated size from rotational diffusion studied using fluorescence depolarization. The implication of this concurrence is that asphaltene molecular structures are monomeric, not polymeric.

Chain of custody for samples of live crude oil using visible-near-infrared spectroscopy.

In order to design oil production facilities and strategies, it is necessary to acquire crude oil samples from subsurface formations in oil wells in so-called openhole prior to production. In some environments, such as deepwater production of oil, decisions of huge economic importance are based on such samples. To date, there has been little quality control to verify that the crude oils collected in the sample bottles and analyzed up to a year later in the laboratory have any relation to the actual crude oils in the subsurface reservoirs. These high-pressure samples can undergo myriad deleterious alterations. Here, we introduce the chain-of-custody concept to the oilfield. The visible-near-infrared spectrum of the crude oil is measured in situ in the wellbore at the point of sample acquisition. This spectrum is compared with the spectrum measured on putatively the same fluid in the laboratory at the start of laboratory sample analysis. First, quantitative assessment is made of whether the fluid in the (high-pressure) sample bottle remains representative of formation fluids. Second, any specific changes in the spectrum of the fluid can be related to possible process control failures. Here, the entire process of chain of custody is proven. The chain of custody process can rapidly become routine in the petroleum industry, thereby significantly improving the reliability of any process that depends on fluid property determination.

High-Q ultrasonic determination of the critical nanoaggregate concentration of asphaltenes and the critical micelle concentration of standard surfactants.

Asphaltenes are known to be interfacially active in many circumstances such as at toluene-water interfaces. Furthermore, the term micelle has been used to describe the primary aggregation of asphaltenes in good solvents such as toluene. Nevertheless, there has been significant uncertainty regarding the critical micelle concentration (CMC) of asphaltenes and even whether the micelle concept is appropriate for asphaltenes. To avoid semantic debates we introduce the terminology critical nanoaggregate concentration (CNAC) for asphaltenes. In this report, we investigate asphaltenes and standard surfactants using high-Q, ultrasonic spectroscopy in both aqueous and organic solvents. As expected, standard surfactants are shown to exhibit a sharp break in sonic velocity versus concentration at known CMCs. To prove our methods, we measured known surfactants with CMCs in the range from 0.010 g/L to 2.3 g/L in agreement with the literature. Using density determinations, we obtain micelle compressibilities consistent with previous literature reports. Asphaltenes are also shown to exhibit behavior similar to that of ultrasonic velocity versus concentration as standard surfactants; asphaltene CNACs in toluene occur at roughly 0.1 g/L, although the exact concentration depends on the specific (crude oil) asphaltene. Furthermore, using asphaltene solution densities, we show that asphaltene nanoaggregate compressibilities are similar to micellar compressibilities obtained with standard nonionic surfactants in toluene. These results strongly support the contention that asphaltenes in toluene can be treated roughly within the micelle framework, although asphaltenes may exhibit small levels of aggregation (dimers, etc.) below their CNAC. Furthermore, our extensive results on known surfactants agree with the literature while the asphaltene CNACs reported here are one to two orders of magnitude lower than most previously published results. (Previous work utilized the terminology "micelle" and "CMC" for asphaltenes.) We believe that the previously reported high concentrations for asphaltene CMCs do not correspond to primary aggregation; perhaps they refer to higher levels of aggregation or perhaps to a particular surface structure.

Diffusional fluorescence quenching of aromatic hydrocarbons.

The quenching of the fluorescence of five aromatic hydrocarbons by three halogenated organics and by molecular oxygen has been measured. Both fluorescence intensity and fluorescence lifetime measurements have been employed to validate results and interpretation; linear Stern-Volmer analyses are shown to apply throughout. The fluorescence quenching rate constant of molecular oxygen for the five aromatic hydrocarbons is essentially equivalent to the diffusion rate constant independent of the fluorophore excitation energy. The halogenated organic-fluorophore rate constants vary by a factor of 965 and are shown to correlate roughly with the energy difference between the quencher and fluorophore excited electronic states in accord with a standard model of quantum two-level mixing. The value of the coupling interaction energy is approximately 2500 cm(-1).