High Molecular Weight Alkanes Research Articles

Selection of representative molecules of asphalt aromatics based on principal component analysis and hierarchical clustering

ABSTRACT Aromatics constitute the highest proportion among the four asphalt components. The existing literature contains over 20 types of small molecules used to characterise asphalt aromatics, which presents a challenge in constructing asphalt molecular models. In this investigation, quantum chemical calculations were employed to determine the molecular morphology, molecular polarity, and infrared spectrum indicators of asphalt aromatics. Based on principal component analysis and hierarchical clustering, statistical analysis of the aforementioned indicators was conducted to present a recommended scheme for selecting representative molecules of aromatics, thereby reducing the difficulty of constructing asphalt molecular models. The results indicated that N2 was recommended as the representative molecule for aromatics with high molecular weight and long alkane chains, while N3 was recommended as the representative molecule for aromatics with low molecular weight. Based on the variations in substituents of aromatics, it was advisable to select one or more of N7, N10, N14 – N16, and N19 as representative molecules. The investigation guided the selection of aromatic representative molecules in the construction of asphalt molecular models. For major projects with test data, representative molecules could be adjusted according to the test data.

Soil processes modify the composition of volatile organic compounds (VOCs) from CO2- and CH4-dominated geogenic and landfill gases: A comprehensive study

Degradation mechanisms affecting non-methane volatile organic compounds (VOCs) during gas uprising from different hypogenic sources to the surface were investigated through extensive sampling surveys in areas encompassing a high enthalpy hydrothermal system associated with active volcanism, a CH4-rich sedimentary basin and a municipal waste landfill. For a comprehensive framework, published data from medium-to-high enthalpy hydrothermal systems were also included. The investigated systems were characterised by peculiar VOC suites that reflected the conditions of the genetic environments in which temperature, contents of organic matter, and gas fugacity had a major role. Differences in VOC patterns between source (gas vents and landfill gas) and soil gases indicated VOC transformations in soil. Processes acting in soil preferentially degraded high-molecular weight alkanes with respect to the low-molecular weight ones. Alkenes and cyclics roughly behaved like alkanes. Thiophenes were degraded to a larger extent with respect to alkylated benzenes, which were more reactive than benzene. Furan appeared less degraded than its alkylated homologues. Dimethylsulfoxide was generally favoured with respect to dimethylsulfide. Limonene and camphene were relatively unstable under aerobic conditions, while α-pinene was recalcitrant. O-bearing organic compounds (i.e., aldehydes, esters, ketones, alcohols, organic acids and phenol) acted as intermediate products of the ongoing VOC degradations in soil. No evidence for the degradation of halogenated compounds and benzothiazole was observed. This study pointed out how soil degradation processes reduce hypogenic VOC emissions and the important role played by physicochemical and biological parameters on the effective VOC attenuation capacity of the soil.

Advanced Treatment of Coking Wastewater by Polyaluminum Silicate Sulfate for Organic Compounds Removal.

Coking wastewater is a typical high-strength organic wastewater, for which it is difficult to meet discharging standards with a single biological treatment. In this study, effective advanced treatment of coking wastewater was achieved by coagulation with freshly prepared polyaluminum silicate sulfate (PASS). The performance advantage was determined through comparison with commercial coagulants including ferric chloride, polyferric sulfate, aluminum sulfate and polyaluminum chloride. Both single-factor and Taguchi experiments were conducted to determine the optimal conditions for coagulation with CODCr and UV254 as indicators. A dosage of 7 mmol/L PASS, flocculation velocity of 75 r/min, flocculation time of 30 min, pH of 7, and temperature of 20 °C could decrease the CODCr concentration from 196.67 mg/L to 59.94 mg/L. Enhanced coagulation could further help to remove the organic compounds, including pre-oxidation with ozonation, adsorption with activated carbon, assistant coagulation with polyacrylamide and secondary coagulation. UV spectrum scanning and gas chromatography-mass spectrometry revealed that the coagulation process effectively removed the majority of organic compounds, especially the high molecular weight alkanes and heterocyclic compounds. Coagulation with PASS provides an effective alternative for the advanced treatment of coking wastewater.

Degradation of LDPE Using the Winogradsky Column Containing Otteri Dumpsite Soil: Prediction of Mechanism and Metabolites Determination

Background of the Research: Plastic pollution has taken over the world. Toxicity of the plastics and other pollutants is enhanced due to the formation of microplastics and nano-plastics that attract Persistent Organic Pollutants (POPs). The need for the treatment of plastic waste in the current scenario led to the rise of various treatment processes. Biodegradation, an eco-friendly approach to eliminate plastics urged to discover plastic-utilizing bacteria and plastic-eating worms. Bacterial degradation of plastics has been extensively studied utilizing the entire microbial community. Hence, the current research focuses on the biodegradation of Low-Density polyethylene (LDPE) using Winogradsky Column constructed using dump yard soil. LDPE degradation was determined using FTIR and GC-MS analysis, which is used to analyze the degradation mechanism of LDPE. Methods: Sample Collection and Column Construction: The soil samples collected from the Chennai dump yard were used to construct Winogradsky columns. The column with LDPE and enrichment sources is used to study LDPE degradation. Analysis of LDPE Degradation: The LDPE sheet after incubation was washed with surfactant and ethanol. The dried sheet was analyzed for weight loss and the metabolites were identified using GC-MS analysis. The GC-MS chromatogram was used to determine the pattern of degradation by the microbial community in the dump yard soil. Results: The mass spectral analysis of GC peaks has been carried out using the electron ionization method, and ions were detected using positive ions scanning mode. The GC peaks appeared at 22.532 and 23.117 min in the control LDPE sheet, which was found to be nonadecane and octacosane, whereas, in the treated LDPE sheet, the GC peaks appeared at 22.467 and 23.062 min. The fragmentation pattern indicates the loss of m/z 14, which confirms the loss of methylene (-CH2-) fragments in alkyl chains. The difference in retention time could be correlated with the increase of CH2 in the alkyl chain length and molecular weight. Higher molecular weight alkanes, such as C16, C18, and C20 above appeared at higher retention times. The presence of longer alkyl chains indicates the LDPE polymer chains. The treated LDPE sample has been analyzed, and the fragmentation pattern indicates the presence of aliphatic chains of C16 or C18. Conclusion: The current study provides an efficient method to utilize the microbial community as a whole to degrade LDPE. The degradation mechanism of LDPE was determined using GC-MS analysis. The high molecular weight polymeric chain was degraded to small chains, and the formation of alcohol indicates the occurrence of terminal oxidation. Hence, this confirms the degradation of LDPE by the microbiome present in the dump yard soil.

FEATURES OF THE DISTRIBUTION AND COMPOSITION OF ORGANIC COMPOUNDS IN WATER AND BOTTOM SEDIMENTS CHERNAVKA RIVER FLOWING INTO ELTON LAKE

Organic compounds: Corg, lipids, hydrocarbons (HCs) – aliphatic (AHCs) and polycyclic aromatic (PAHs) in suspended particulate matter of surface waters and in bottom sediments of the shallow Chernavka River, which flows into a self-sustaining Elton Lake were studied. High concentrations of organic compounds were found in surface waters: in averaged 692, 80 and 0.79 µg/L for lipids, AHCs, and PAHs respectively. The composition of alkanes in the aqueous suspension corresponded to the weathered oil hydrocarbons. HC transformation occurs here not in the course of sedimentation, but at the water–bottom sediment interface. As a result, the AHC composition of the sediments differed from that of the particulate matter in the presence of planktonogenic low molecular weight homologues of n C15–C17 and a sharp increase in the series of odd high molecular weight alkanes, while the PAH composition differed in the increase in the proportion of naphthalene.

Cationic Tantalum Hydrides Catalyze Hydrogenolysis and Alkane Metathesis Reactions of Paraffins and Polyethylene.

Sulfated aluminum oxide (SAO), a high surface area material containing sulfate anions that behave like weakly coordinating anions, reacts with Ta(═CHtBu)(CH2tBu)3 to form [Ta(CH2tBu)2(O-)2][SAO] (1). Subsequent treatment with H2 forms Ta-H+ sites supported on SAO that are active in hydrogenolysis and alkane metathesis reactions. In both reactions Ta-H+ is more active than related neutral Ta-H sites supported on silica. This reaction chemistry extends to melts of high-density polyethylene (HDPE), where Ta-H+ converts 30% of a low molecular weight HDPE (Mn = 2.5 kg mol-1; Đ = 3.6) to low molecular weight paraffins under hydrogenolysis conditions. Under alkane metathesis conditions Ta-H+ converts this HDPE to a high MW fraction (Mn = 6.2 kDa; Đ = 2.3) and low molecular weight alkane products (C13-C32). These results show that incorporating charge as a design element in supported d0 metal hydrides is a viable strategy to increase the reaction rate in challenging reactions involving reorganization of C-C bonds in alkanes.

Hydrocarbon composition of liquid products of catalytic oxy-cracking of vacuum gasoil

The hydrocarbon composition of liquid products of oxycracking of vacuum gas oil obtained in the presence of a zeolite-containing catalyst has been studied. It has been established that the group hydrocarbon composition of the liquid oxycracking catalyzate is significantly affected by the process parameters. When considering the influence of the process temperature, it was found that the concentration of C5-C9 and C10+ alkanes has an opposite temperature dependence: the C5-C9 yield passes through a maximum at a temperature of 500°C, while for C10+ it is a minimum temperature; there is a linear relationship between the temperature and the yield of unsaturated; the yield of naphthenes gradually decreases with increasing temperature; elevated temperatures contribute to an increase in the total yield of aromatic hydrocarbons. When varying the duration of the process, it was revealed: within 900 seconds from the beginning of the process, the most significant decrease in concentration was noted for aromatic hydrocarbons. The low oxidation state of 0.5% contributes to the intensive conversion of high molecular weight alkanes and aromatic hydrocarbons with long side chains; the concentration of oxygen-containing compounds raises with an increase in the degree of oxidation to 1%, passing through a maximum. The contact time with the catalyst had a complex effect on the hydrocarbon composition of the liquid products of vacuum gas oil oxycracking: a short contact time contributes to a decrease in the concentration of high molecular weight paraffinic and naphthenic hydrocarbons and an increase in aromatic hydrocarbons; with a subsequent increase to 2 s, it drops sharply. The obtained data made it possible to establish the fundamental distinguishing features of the catalytic oxycracking of vacuum gas oil from the traditional catalytic and noncatalytic oxidative ones, and also to propose a list of reactions occurring during the catalytic oxycracking of vacuum gas oil.

Investigating the Influence of n-Heptane versus n-Nonane upon the Extraction of Asphaltenes.

The composition of asphaltenes is of interest due to the challenges they pose for industry and their high complexity, encompassing a range of heteroatom contents, molecular weights, double bond equivalents (DBEs), and structural motifs. They are well-known for aggregating above critical concentrations, hindering the upstream and downstream processes. Asphaltenes are defined by solubility, as they are insoluble in light paraffins such as n-heptane and soluble in aromatic solvents such as toluene. Today, enormous efforts are being invested into the characterization of asphaltenes to shed light into their structural profiles to benefit the petroleum industry and environmental sustainability. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides molecular level analysis with unparalleled mass resolving power and mass accuracy, which is vital for the characterization of inherently complex crude oils and their asphaltene fractions. The aim of this research is to elucidate and compare the compositional profiles of asphaltene fractions of two petroleum samples, fractioned through two approaches: using n-heptane, as is typical practice, and n-nonane, for the purpose of testing extraction using higher molecular weight alkanes. The results highlight that the choice of solvents does indeed influence the accessibility of different species and therefore changes the observed molecular profiles of the extracted asphaltenes. n-Heptane afforded broader contributions of different heteroatomic classes and greater carbon number ranges of the observed components; the DBE distribution vs carbon number profiles were different, where the extracts produced using n-nonane displayed a greater prevalence of lower DBE species.

Origin and environmental implications of dibenzothiophenes in the Huanghekou East Sag and the Laizhouwan Northeast Sag, Bohai Bay Basin

A suite of nine oils from Huanghekou East Sag and Laizhouwan Northeast Sag, Bohai Bay Basin, China, were analysed to investigate the effect of the depositional environment on dibenzothiophenes. Five oils were high-sulfur oils (HSOs, sulfur content >1%) from Huanghekou East Sag while other four oils were low-sulfur oils (LSOs). The major organic matter inputs of all oils were algae, and specific algae might contribute to the high molecular weight alkanes and C29 steranes of HSOs. HSOs mainly originated from carbonate-rich source rocks in more saline environments while LSOs derived from clay-rich source rocks deposited in freshwater conditions, as supported by a series of biomarkers, including phytane, gammacerane, terpanes and their abundance ratios. Maturity parameters show that the samples are all in the low mature to mature stage. The methylated dibenzothiophenes are more abundant in HSOs than those in LSOs. The major sources of methylated dibenzothiophenes are algae and bacteria while the dibenzothiophene is more derived from terrigenous plants, according to the carbon isotope values of individual compounds. Abundant bacterially generated H2S as well as reducing depositional environment result in transformation from algae-originated organic matter to relatively large amount of dibenzothiophenes, further, carbonate-rich source rocks might inhibit the demethylation, leading to the more abundance of methylated dibenzothiophenes in HSOs. Parameters derived from dibenzothiophenes, such as the ratios: methyldibenzothiophenes/methylphenanthrenes, methyldibenzothiophenes/phenanthrenes, dimethyldibenzothiophenes/dimethylphenanthrenes, and dimethyldibenzothiophenes/phenanthrenes are most useful for indicating reducing depositional environments among HSOs and LSOs.

Evolution of nC16H34-water–mineral systems in thermal capsules and geological implications for deeply-buried hydrocarbon reservoirs

Organic-inorganic interactions between hydrocarbons and most minerals in deeply buried reservoirs remain unclear. In this study, gold capsules and fused silica capillary capsules (FSCCs) with different combinations of nC16H34, water (distilled water, CaCl2 water) and minerals (quartz, feldspar, calcite, kaolinite, smectite, and illite) were heated at 340 °C for 3–10 d, to investigate the evolution and reaction pathways of the organic–inorganic interactions in different hot systems.After heating, minerals exhibited little alteration in the anhydrous systems. Mineral alterations, however, occurred obviously in the hydrous systems. Different inorganic components affected nC16H34 degradation differently. Overall, water promoted the free-radical thermal-cracking reaction and step oxidation reaction but suppressed the free-radical cross-linking reaction. The impact of CaCl2 water on the nC16H34 degradation was weaker than the distilled water as high Ca2+ concentration suppressed the formation of free radicals. The presence of different waters also affects the impact of different minerals on nC16H34 degradation, via its impact on mineral alterations. In the anhydrous nC16H34-mineral systems, calcite and clays catalyzed generation of low-molecular-weight (LMW) alkanes, particularly the clays. Quartz, feldspar, and calcite catalyzed generation of high-molecular-weight (HMW) alkanes and PAHs, whereas clays catalyzed the generation of LMW alkanes and mono-bicyclic aromatic hydrocarbons (M-BAHs). In the hydrous nC16H34-distilled water–mineral systems, all minerals but quartz promoted nC16H34 degradation to generate more LMW alkanes, less HMW alkanes and PAHs. In the nC16H34-CaCl2 water–mineral systems, the promotion impact of minerals was weaker than that in the systems with distilled water.This study demonstrated the generation of different hydrocarbons with different fluorescence colors in the different nC16H34-water–mineral systems after heating for the same time, implying that fluorescence colors need to be interpreted carefully in investigation of hydrocarbon charging histories and oil origins in deeply buried reservoirs. Besides, the organic–inorganic interactions in different nC16H34-water–mineral systems proceeded in different pathways at different rates, which likely led to preservation of liquid hydrocarbons at different depth (temperature). Thus, quantitative investigations of the reaction kinetics in different hydrocarbon-water-rock systems are required to improve the prediction of hydrocarbon evolution in deeply buried hydrocarbon reservoirs.

Comparative study of a vitrinite-rich and an inertinite-rich Witbank coal (South Africa) using pyrolysis-gas chromatography

This study aims to compare iso-rank vitrinite-rich and inertinite-rich coal samples to understand the impact of coal-forming processes on pyrolysis chemistry. A medium rank C bituminous coal was density-fractionated to create a vitrinite-rich and an inertinite-rich sub-sample. The vitrinite-rich sample has 83 vol% total vitrinite (mineral-matter-free basis), whereas the inertinite-rich counterpart has 66 vol% total inertinite. The vitrinite-rich sample is dominated by collotelinite and collodetrinite. Fusinite, semifusinite, and inertodetrinite are the main macerals of the inertinite-rich sample. Molecular chemistry was assessed using a pyrolysis gas chromatograph (py-GC) equipped with a thermal desorption unit coupled to a time of flight mass spectrometer (MS) (py-GC/MS) and solid-state nuclear magnetic resonance (13C CP-MAS SS NMR). The pyrolysis products of the coal samples are generally similar, comprised of low and high molecular weight alkanes, alkylbenzenes, alkylphenols, and alkyl-subtituted polycyclic aromatic hydrocarbons, although the vitrinite-rich sample is chemically more diverse. The lack of diversity exhibited by the inertinite-rich sample upon pyrolysis may be interpreted to suggest that major components were heated in their geologic history. Based on the 13C CP-MAS SS NMR analysis, the inertinite-rich sample has a greater fraction of phenolics, reflected in the py-GC/MS results as substituted and unsubstituted derivatives. The greater abundance of phenolics for the inertinite-rich sample may suggest a fire-related origin for the dominant macerals of this sample. The C2-alkylbenzene isomers (p-xylene and o-xylene) were detected in the pyrolysis products for the vitrinite-rich and inertinite-rich samples, though more abundant in the former. The presence of these in both samples likely reflects common source vegetation for the dominant vitrinite and inertinite macerals.

First Investigation of Seasonal Concentration Behaviors and Sources Assessment of Aliphatic Hydrocarbon in Waters and Sediments from Wadi El Bey, Tunisia.

The contents, composition profiles, and sources of aliphatic hydrocarbons were examined in surface sediment and water samples collected from Wadi El Bey, in Tunisia, during different year seasons in 14 stations receiving domestic effluent, industrial discharge, and agricultural drainage wastes. The target substances were analyzed by gas chromatography coupled with mass spectrometric detection (GC/MS). Total concentrations of n-alkanes (n-C14-n-C38) ranged from 0.08 ± 0.01 to 18.14 ± 0.1µg/L in waters and 0.22 ± 0.04 to 31.9 ± 24.6µg/g in sediments, while total aliphatic fraction ranged from 0.08 ± 0.01 to 196 ± 140µg/L in waters and 0.22 ± 0.04 to 1977 ± 1219µg/g in sediments, which means that almost all sites were affected by hydrocarbon contents in sediments exceeding the recommended limit (100µg/g). Various diagnostic indices (ADIs) were used to identify the hydrocarbon sources, namely the concentration ratios of individual compounds (n-C17/pristane, n-C18/phytane, pristane/phytane, n-C29/n-C17, n-C31/n-C19) as well as cumulative quantities (Carbon Preference Index, natural n-alkanes ratio, terrigenous/aquatic compounds ratio, unresolved complex mixture percentage, low molecular weight vs. high molecular weight homologues, Alkane Proxy and Terrestrial Marine Discriminants). In general, these indexes indicated that the origin of aliphatic hydrocarbons affecting sediments and waters of Wadi El Bey were linked to both biogenic and petrogenic inputs, attesting the impact of plankton and terrestrial plants and of oil contamination, respectively. The average carbon chain length computation (ACL), used to further index the chemical environment, ranged from 25.5 to 31.1 in sediments and 47.9-116 in waters. This finding could depend on the severe disturbances suffered by the ecosystem as a consequence of heavy anthropogenic inputs. Petroleum contamination associated with high eutrophication rates in Wadi El Bey must be strictly controlled, due to possible harmful effects induced on ecosystem and humans.

Solvent-pore interactions in the Eagle Ford shale formation

The effect of solvent extraction on pore space was examined on a suite of samples from the Eagle Ford Shale Formation with varying lithologies and maturities. Several solvents ─toluene, cyclohexane, methanol, dichloromethane, and hydrochloric acid─ were contacted with shale samples, extracting the compatible organic matter. The porosity in these extracted shale samples was compared to unmodified samples. The amount and type of organic matter extracted were determined using Gas Chromatography ─ Mass Spectrometry, and the porosity was determined by (Ultra) Small Angle Neutron Scattering. Mostly alkanes and aromatics were detected in the extracts, but other portions of bitumen may also have been present. Only higher molecular weight alkanes were extracted with hydrochloric acid, suggesting that physical dissolution of carbonate minerals may have liberated this portion of organic matter and the solvent was not able to penetrate the bitumen and kerogen to extract the lower molecular weight alkanes. Additionally, a decrease in porosity with extraction was observed and attributed to a dominant mechanism of kerogen swelling due to kerogen-solvent interaction.

Lipid biomarkers in Lake Enol (Asturias, Northern Spain): Coupled natural and human induced environmental history

The lipid content of three cores from Lake Enol (Picos de Europa National Park, Asturias, Northern Spain) was studied. The n-alkane profiles indicated a major input from terrigenous plants [predominance of high molecular weight (HMW) alkanes] since ca. 1695 AD to the water body, although the uppermost cm revealed a predominance of organic matter (OM) derived from algae, as the most abundant alkane was C17. Three units revealing different environmental conditions were defined. Unit A (ca. 1695–1860 AD) in the lowermost parts of ENO13-10 (<12cm) and ENO13-15 (<28cm) was identified and was characterized by higher OM input and evidence of minimal degradation (high CPI values, predominance of HMW n-alkanoic acids and good correspondence between the predominant n-alkane and n-alkanoic acid chains). These findings could be linked to the Little Ice Age, when cold and humid conditions may have favored an increase in total organic carbon (TOC) and n-alkane and n-alkanoic acid content (greater terrigenous OM in-wash), and may have also reduced bacterial activity. In Unit B (ca. 1860–1980 AD) the lack of correspondence between the n-alkane and n-alkanoic acid profiles of ENO13-10 (12–4cm) and ENO13-15 (28–8cm) suggested a certain preferential microbial synthesis of long chain saturated fatty acids from primary OM and/or bacterial activity, coinciding with a decrease in OM input, which could be linked to the global warming that started in the second half of the 19th century. In ENO13-7 the low OM input (low TOC) was accompanied by some bacterial degradation (predominance of HMW n-alkanoic acids but with a bimodal distribution) in the lowermost 16–5cm. Evidence of considerable phytoplankton productivity and microbial activity was especially significant in Unit C (ca. 1980–2013 AD) identified in the uppermost part of all three cores (5cm in ENO13-7, 4cm in ENO13-10 and 8cm in ENO13-15), coinciding with higher concentrations of n-alkanes and n-alkanoic acids, which were considered to be linked to warmer and drier conditions, as well as to greater anthropogenic influence in modern times.Plant sterols, such as β-sitosterol, campesterol and stigmasterol, were significantly present in the cores. In addition, fecal stanols, such as 24-ethylcoprostanol from herbivores, were present, thereby indicating a continuous and significant pollution input derived from these animals since the 17th century, being more important in the last 20years.

Ab Initio Crystallization of Alkanes: Structure and Kinetics of Nuclei Formation

Molecular dynamics simulations of the crystallization of eicosane have been carried out as an example of a low molecular weight n-alkane system and for a high molecular weight alkane as an analogue of a semicrystalline polyethylene. An alternative method for determining crystal domains and growing nuclei has been developed based on the eicosane system behavior. In the former case, density and crystal lattice parameters conformed well to previously reported experimental values. Moreover, crystallization and nuclei formation were monitored using a procedure developed herein. Analysis showed that metastable nuclei could be obtained at 250 K lasting appreciably long lifetimes of tens to hundreds of nanoseconds, which then exhibited an abrupt irreversible increase in size. The present study emphasizes the long quasi-equilibrium of these crystallizing systems even at moderate supercooling.

Selective conversion of butane into liquid hydrocarbon fuels on alkane metathesis catalysts

We report a selective direct conversion of n-butane into higher molecular weight alkanes (C5+) by alkane metathesis reaction catalysed by silica–alumina supported tungsten or tantalum hydrides at moderate temperature and pressure. The product is unprecedented, asymmetrically distributed towards heavier alkanes.

Changes in iso- and n-alkane distribution during biodegradation of crude oil under nitrate and sulphate reducing conditions

Crude oil consists of a large number of hydrocarbons with different susceptibility to microbial degradation. The influence of hydrocarbon structure and molecular weight on hydrocarbon biodegradation under anaerobic conditions is not fully explored. In this study oxygen, nitrate and sulphate served as terminal electron acceptors (TEAs) for the microbial degradation of a paraffin-rich crude oil in a freshly contaminated soil. During 185 days of incubation, alkanes from n-C11 to n-C39, three n- to iso-alkane ratios commonly used as weathering indicators and the unresolved complex mixture (UCM) were quantified and statistically analyzed. The use of different TEAs for hydrocarbon degradation resulted in dissimilar degradative patterns for n- and iso-alkanes. While n-alkane biodegradation followed well-established patterns under aerobic conditions, lower molecular weight alkanes were found to be more recalcitrant than mid- to high-molecular weight alkanes under nitrate-reducing conditions. Biodegradation with sulphate as the TEA was most pronounced for long-chain (n-C32 to n-C39) alkanes. The observation of increasing ratios of n-C17 to pristane and of n-C18 to phytane provides first evidence of the preferential degradation of branched over normal alkanes under sulphate reducing conditions. The formation of distinctly different n- and iso-alkane biodegradation fingerprints under different electron accepting conditions may be used to assess the occurrence of specific degradation processes at a contaminated site. The use of n- to iso-alkane ratios for this purpose may require adjustment if applied for anaerobic sites.

High molecular weight waxes from Short Path Distillates of vacuum residue

Short Path Distillates of vacuum residue (boiling above 545 °C) is taken as feedstock for this study. Wax from this fraction is separated by solvent extraction method using methyl iso-butyl ketone (MIBK) as solvent. Both wax and the feedstock are characterised with the help of ASTM and IP procedures. Separated wax is fractionated at different temperatures, say 0–30 °C using MIBK as solvent. High temperature gas chromatography (HTGC) technique is used to study the distribution of alkane carbon number in all the fractions. It is observed that the wax contains very high molecular weight hydrocarbons as high as C 67H 136. HTGC technique as well as the Differential Scanning Calorimetry (DSC) indicates that all the fractions of the wax contain two types of hydrocarbons, one having high molecular weight alkanes (> 600) and another having low mol. wt. alkanes (~ 400). Thermal analysis by DSC technique further indicates that the wax is microcrystalline in nature having a low degree of crystallinity, 17%, as evidenced by XRD studies. Both high and low molecular weight waxes can also be separated based on their solubility characteristics.

Equation of State for the Phase Behavior of Carbon Dioxide−Polymer Systems

We proposed a hybrid equation of state for CO2−polymer systems that utilizes the Peng−Robinson (PR) equation of state for the molecular excluded-volume effects and the van der Waals attractions, and equations from the statistical associating fluid theory (SAFT) for the polymer intrachain correlations and for the short-ranged forces due to weakly polar or association interactions. The numerical performance of the new equation of state was tested by its application to correlating the PVT behavior of pure CO2, including both the vapor−liquid coexistence densities, the vapor pressure, and the specific density of condensed CO2 at near-critical and supercritical conditions, and to the volumetric properties of high molecular weight alkanes and a few representative polymers. With the parameters from the original PR equation of state for nonpolar monomeric fluids and additional ones to account for the solvent polarity and the solute degree of polymerization, the new equation of state was successfully used to calcu...

Biodegradation of semi- and non-volatile petroleum hydrocarbons in aged, contaminated soils from a sub-Arctic site: Laboratory pilot-scale experiments at site temperatures

This study evaluates the feasibility of landfarming biotreatment of petroleum-contaminated soils obtained from a sub-Arctic site at Resolution Island, Nunavut, Canada, and evaluates the changes in composition of the semi- and non-volatile petroleum hydrocarbon fractions during the biotreatment. Pilot-scale landfarming experiments were conducted in a laboratory in soil tanks under temperature profiles representative of the 3-year site air temperatures in July and August where temperature varied uniformly between 1 °C and 10 °C over 10 d. The site soils were acidic and N-deficient, but contained indigenous populations of hydrocarbon-degrading microorganisms. Biostimulation with nitrogen and phosphorus nutrient amendments to achieve C TPH:N:P molar ratio of 100:9:1, and CaCO 3 amendment at 2000 mg Kg −1 for maintaining neutral pH, and periodic 10-day tilling, reduced total petroleum hydrocarbon (TPH) concentrations by up to 64% over a 60-day period. The rate and extent of semi-volatile (F2: >C10–C16) and non-volatile (F3: >C16–C34) petroleum hydrocarbon fractions in the landfarms containing higher initial TPH levels (∼2000 mg Kg −1) and lower TPH levels (∼1000 mg Kg −1) were compared. Significant biodegradation of the F2 and F3 fractions occurred in both of those systems. First-order biodegradation rate constants of up to 0.019 ± 0.001 d −1 were determined for the F3 hydrocarbon fraction and were similar to the F2 fraction biodegradation rate constants of up to 0.024 ± 0.005 d −1. Biodegradation profiles of the C14, C16 and C18 alkanes revealed that at TPH concentrations above 1000 mg Kg −1 these compounds are degraded concurrently, whereas below 1000 mg Kg −1 the higher-molecular weight alkanes are preferentially degraded. After the 60-day treatment period, the TPH concentration was approximately 500 mg Kg −1, and the residual TPH mass was largely associated with particles and aggregated particles with diameters of 0.6–2 mm, rather than the larger or finer particles and aggregates.