Complex Mixture Of Hydrocarbons Research Articles

ESTUDO DE GASOLINAS PREMIUM E COMUM COMERCIALIZADAS NO BRASIL ATRAVÉS DO MÉTODO ERETIC-RMN E QUIMIOMETRIA

STUDY OF PREMIUM AND REGULAR GASOLINES MARKETED IN BRAZIL THROUGH THE ERETIC-NMR METHOD AND CHEMOMETRICS. Gasoline is a complex mixture of hydrocarbons whose detailed study of its chemical profiles is a challenging task. This type of product of great commercial importance has its quality measured in Brazil from classical physicalchemical tests. Although robust, physical-chemical analyses generally require large amounts of assays, solvents, and samples, in addition to not being indicated for the detection of small compositional changes. In this work, NMR and chemometrics were used in the quantitative study of different samples of gasoline with varying ratings of octane and ethanol contents. The results demonstrated the usefulness of NMR spectroscopy both to characterize as well as to distinguish the chemical profiles of regular and premium gasoline. With the application of the ERETIC, the chemical profiles mentioned were quantitatively differentiated and the proportions between hydrocarbons were determined for both types of gasoline. The application of the ERETIC was also successful in the quantitative determination of ethanol contents in regular and premium gasoline. The aforementioned method, which dispenses with the use of quantification standards inserted directly into the sample of interest, was unequivocal in accounting for the volume of ethanol, in addition to showing excellent agreement with the method currently adopted by the Brazilian government.

Оценка параметра растворимости Гильдебранда смеси растворителей нефтяного происхождения по их структурным элементам

The work is devoted to the methodological aspects of estimating the Hildebrand solubility parameter of a mixture of organic solvents using the characteristics of their structural elements. A method is proposed for calculating the solubility parameter for mixtures of solvents that differ in composition and structure depending on the ratio of components. The results of calculations make it possible to predict the optimal composition of solvent mixtures for polymers with a known Hildebrand solubility parameter. The proposed method makes it possible to estimate the solubility parameter of complex mixtures of hydrocarbons of petroleum origin, for example, the vacuum residue of oil distillation - goudron, when it is used as a polymer solvent. Based on the results of 1H NMR analysis,the structural elements of goudron were determined and its Hildebrand solubility parameter was calculatedn.

Про закономірність природних процесів синтезу і генезису вуглеводнів та води нафтових і газових родовищ: абіогенно-біогенний дуалізм

It is shown that the problem of the nature of water in oil and gas fields must be solved in an inextricable connection with the genesis and synthesis of natural hydrocarbons in the Earth’s bowels. The work offers an original solution, based on a new theory of the synthesis and genesis of hydrocarbons (oil, gas, etc.): abiogenic-biogenic dualism, which asserts that giant and supergiant oil and gas fields were formed from inorganic and organic original hydrocarbon-containing substances under the influence of abiogenic high-thermobaric deep fluid in harsh physical, physicochemical and geological conditions of the earth’s crust. Since the abiogenic high-thermobaric deep fluid contains hydrogen H+ and OH-containing anions, the described mechanism for the interaction of positively charged ions: C+, H+, CnHm+-radicals with the formation-synthesis of a complex hydrocarbon mixture such as gas, oil, bitumen, etc. must be logically supplemented by a reaction: H2O → H+ + ОН−. As a result of this complex physical and chemical process, the maximum concentration of (OH−) anions accumulated in the oxidation zone, which after the disappearance of the electric field become neutral and interact with each other according to the scheme: ОН + ОН = H2O2 – hydrogen peroxide, which is an unstable compound, which decomposes into H2O + О. Oxygen atoms became the starting substances for the formation of macro- and microcracks in these cavities under harsh conditions of rocks of the carbonate or quartz-carbonate type, etc., much less often – perfect mineral crystals, which with their defects in the process of growth (synthesis) captivate and preserve substances in the system (proper hydrocarbons and water). Therefore, it was established for the first time that the natural water of oil and gas fields has a dual lithospheric-asthenospheric nature, while the lithospheric part is dominant, the isotopic composition is a mixture of these waters, and the deuterium isotope is more chemically active in complex physical and chemical processes, which run through the bowels of the planet. The obtained original data will contribute to the solution of Ukraine’s serious problem with energy carriers: natural gas, oil, coal and drinking water.

Sterane and hopane biomarkers capture microbial transformations of complex hydrocarbons in young hydrothermal Guaymas Basin sediments

In Guaymas Basin, organic-rich hydrothermal sediments produce complex hydrocarbon mixtures including saturated, aromatic and alkylated aromatic compounds. We examined sediments from push cores from Guyamas sites with distinct temperature and geochemistry profiles to gain a better understanding on abiotic and biological hydrocarbon alteration. Here we provide evidence for biodegradation of hopanoids, producing saturated hydrocarbons like drimane and homodrimane as intermediate products. These sesquiterpene by-products are present throughout cooler sediments, but their relative abundance is drastically reduced within hotter hydrothermal sediments, likely due to hydrothermal mobilization. Within the sterane pool we detect a trend toward aromatization of steroidal compounds within hotter sediments. The changes in hopane and sterane biomarker composition at different sites reflect temperature-related differences in geochemical and microbial hydrocarbon alterations. In contrast to traditionally observed microbial biodegradation patterns that may extend over hundreds of meters in subsurface oil reservoirs, Guaymas Basin shows highly compressed changes in surficial sediments.

Characterization of new diesel-degrading bacteria isolated from freshwater sediments.

As the result of diesel's extensive production and use as fuel for transportation, pollution with such complex mixtures of hydrocarbons is a major concern worldwide. The present study's focus was to investigate the presence of diesel-degrading bacteria in different Danube Delta freshwater sediments. Ten bacterial strains capable to grow in a minimal medium with diesel as the sole carbon source were isolated and characterized in this study. Based on the phenotypic and molecular characteristics, the ten strains belong to four genera and seven species, such as Pseudomonas (P. aeruginosa, P. nitroreducens, P. resinovorans, P. multiresinivorans), Acinetobacter (A. tandoii), Bacillus (B. marisflavi), and Stenotrophomonas (S. maltophilia). All these bacteria were excellent biosurfactant producers, and they were able to tolerate saturated hydrocarbons, like n-heptane, n-decane, n-pentadecane, and n-hexadecane. The ten strains possess at least one alkane hydroxylase gene in their genome, and they were also able to tolerate and degrade diesel. Higher biodegradation rates of diesel were acquired for the strains from the genera Pseudomonas, Acinetobacter, and Stenotrophomonas, compared with that obtained for the Bacillus strain. Due to their remarkable potential to degrade diesel and produce biosurfactants, the ten isolated bacteria are attractive candidates for bioremediation of diesel-polluted environments.

Mineral oil contamination in basil pesto from the Italian market: Ingredient contribution and market survey

Mineral oil hydrocarbons (MOH) are complex mixtures of saturated hydrocarbons (MOSH) which bioaccumulate in human tissues, and aromatic hydrocarbons (MOAH) which include genotoxic and carcinogenic substances. This work aimed to investigate these emerging food contaminants in basil pesto from the Italian market, and ingredient contribution to the final product contamination. Twelve market samples and 4 additional samples (and related ingredients) produced in a pilot plant, were analyzed by on-line high-performance liquid chromatography (HPLC)- gas chromatography (GC), preceded by matrix-tailored sample preparation. Method performance was good with recoveries from 94% to 109%, residual standard deviations (RSD) less than 10%, and a limit of quantitation (LOQ) of 0.5 mg/kg (for total MOAH). Vegetable oils, followed by cashews, which showed a similar contamination profile to foods transported in jute bags, were the major contributors to contamination, while cheese and basil contribution was negligible. Sunflower oil alone accounted for more than 80–85% of the total contamination. Samples from the Italian market had an average of 5.6 and 0.6 mg/kg of MOSH and MOAH, respectively, and a contamination profile that confirmed that the main contributors to total contamination were sunflower oil and cashews. Mitigation actions should be directed toward careful control of these two ingredients.

Effects of chromium (VI) on the toxicity of benzo[z]pyrene in 16HBE cells.

Contamination of human habitats with complex mixtures of heavy metals and polycyclic aromatic hydrocarbons (PAHs) is an important environmental and industrial health problem. Hexavalent chromium (Cr(VI)) and benzo(a)pyrene (B[a] P) are typical of the two, respectively. In recent decades, a great deal of research has focused on their carcinogenicity and mechanisms of action. However, few studies have been conducted to evaluate their combined effects on humans and cells, which has important implications for overall understanding of their toxicity and interaction. In the current study, the combined toxic effects of B[a] P and Cr(VI) were studied in human bronchial epithelial cells (16 HBE). We measured the genotoxic activity and epigenetic changes of these two toxicants alone and in combination on these cells and analyzed the difference between their single and combined toxicity. The results showed that B[a]P caused DNA damage in 16HBE cells in a concentration-dependent manner, while the presence of Cr(VI) showed a sharp decrease in DNA damage, and it inhibited the expression of genes related to base excision repair induced by B[a]P. In addition, Cr(VI) also reduced B[a]P-triggered epigenetic changes in 16HBE cells. In conclusion, the combined effect of B[a]P and Cr(VI) on 16HBE cells was less toxic than single B[a]P exposure, indicating that the combined toxicity of the two toxicants is partially antagonistic. Further research is required to explore the mechanism of this antagonism.

Why do ants differ in acclimatory ability? Biophysical mechanisms behind cuticular hydrocarbon acclimation across species.

Maintaining water balance is vital for terrestrial organisms. Insects protect themselves against desiccation via cuticular hydrocarbons (CHCs). CHC layers are complex mixtures of solid and liquid hydrocarbons, with a surprisingly diverse composition across species. This variation may translate into differential phase behaviour, and hence varying waterproofing capacity. This is especially relevant when temperatures change, which requires acclimatory CHC changes to maintain waterproofing. Nevertheless, the physical consequences of CHC variation are still little understood. We studied acclimatory responses and their consequences for CHC composition, phase behaviour and drought survival in three congeneric ant species. Colony sub-groups were kept under cool, warm and fluctuating temperature regimes. Lasius niger and Lasius platythorax, both of which are rich in methyl-branched alkanes, showed largely predictable acclimatory changes of the CHC profile. In both species, warm acclimation increased drought resistance. Warm acclimation increased the proportion of solid compounds in L. niger but not in L. platythorax. In both species, the CHC layer formed a liquid matrix of constantly low viscosity, which contained highly viscous and solid parts. This phase heterogeneity may be adaptive, increasing robustness to temperature fluctuations. In Lasius brunneus, which is rich in unsaturated hydrocarbons, acclimatory CHC changes were less predictable, and warm acclimation did not enhance drought survival. The CHC layer was more homogeneous, but matrix viscosity changed with acclimation. We showed that ant species use different physical mechanisms to enhance waterproofing during acclimation. Hence, the ability to acclimate, and thus climatic niche breadth, may strongly depend on species-specific CHC profile.

Synthetic Saccharomyces cerevisiae tolerate and degrade highly pollutant complex hydrocarbon mixture

Fungal laccase (Lac) has become a very useful biocatalyst in different industries, bio-refineries and, most importantly, bioremediation. Many reports have also linked hydrocarbon tolerance and degradation by various microorganisms with Lac secretion. In this study, Trametes trogii Lac (Ttlcc1) was engineered into Saccharomyces cerevisiae strain CEN.PK2–1 C under the constitutive GPD promoter (pGPD) for multi-fold synthesis with efficient hydrocarbon tolerance and degradation. Protein expression in heterologous hosts is strictly strain-specific, it can also be influenced by the synthetic design and culture conditions. We compared synthetic designs with different shuttle vectors for the yeast strains and investigated the best culture conditions by varying the pH, temperature, carbon, nitrogen sources, and CuSO4 amount. Two S. cerevisiae strains were built in this study: byMM935 and byMM938. They carry the transcription unit pGPD-Ttlcc1-CYC1t either inside the pRSII406 integrative plasmid (byMM935) or the pRSII426 multicopy plasmid (byMM938). The performance of these two synthetic strains were studied by comparing them to the wild-type strain (byMM584). Both byMM935 and byMM938 showed significant response to different carbon sources (glucose, galactose, lactose, maltose, and sucrose), nitrogen sources (NH4Cl, NH4NO3, KNO3, malt extract, peptone, and yeast extract), and solid state fermentation of different plant biomasses (bagasse, banana peels, corn cob, mandarin peels, and peanut shells). They performed best in optimized growth conditions with specific carbon and nitrogen sources, and a preferred pH in the range 3.5–4.5, temperature between 30 and 40 0C, and 1 mM CuSO4. In optimized yeast-growth medium, strain byMM935 showed the highest laccase activities of 1.621 ± 0.063 U/mL at 64 h, whereas byMM938 gave its highest activity (1.417 ± 0.055 U/mL) at 48 h. In this work, we established, by using Bushnell Hass synthetic medium, that the new Ttlcc1-yeast strains tolerated extreme pH and complex hydrocarbon mixture (CHM) toxicity. They degraded 60–90% of the key components in CHM within 48 h, including poly-cyclic aromatic hydrocarbons, alkyl indenes, alkyl tetralines, alkyl benzenes, alkyl biphenyls, and BTEX (Benzene, Toluene, Ethylbenzene, and Xylenes). This is the first report on the hydrocarbon degradation potential of a Ttlcc1-yeast. Compared to the native organism, such synthetic strains are better suited for meeting growing demands and have potentials for application in large-scale in situ bioremediation of hydrocarbon-polluted sites.

Measurement and modeling of methane diffusion in hydrocarbon mixtures

Methane (CH4) dissolution and diffusive mass transfer in liquid hydrocarbon mixtures is of key interest in the context of enhanced oil recovery from tight shales. In this paper, we have studied CH4 dissolution and diffusion in normal alkane mixtures at a temperature of 50 ⁰C and at pressures of ∼8 MPa. For the measurement of CH4 dissolution/diffusion in bulk liquid hydrocarbon mixtures, we have utilized a high pressure and temperature, constant-volume diffusion (CV-D) setup. We have studied CH4 diffusion in mixtures with three long-chain normal alkanes: decane (C10), dodecane (C12) and hexadecane (C16). We have measured CH4 solubility and diffusion in its binary mixtures with each of these three normal alkanes, as well as in ternary and quaternary mixtures. During the experiments, the swelling of the liquid mixture due to CH4 dissolution was measured in situ via a cathetometer and was subsequently integrated into the data analysis. A key conclusion from this study is that the solubility and transport properties of the multicomponent mixtures can be predicted accurately from binary mixture measurements using an appropriate Equation of State (EOS) and Wilke’s simplification of the classical Maxwell-Stefan (MS) diffusion theory. This observation can facilitate accurate prediction of diffusive mass transfer in more complex liquid hydrocarbon mixtures.

Isolation and Screening from Soil Biodiversity for Fungi Involved in the Degradation of Recalcitrant Materials.

Environmental pollution is an increasing problem, and identifying fungi involved in the bioremediation process is an essential task. Soil hosts an incredible diversity of microbial life and can be a good source of these bioremediative fungi. This work aims to search for soil fungi with bioremediation potential by using different screening tests. Mineral culture media supplemented with recalcitrant substances as the sole carbon source were used as growth tests. First, soil dilutions were plated on Petri dishes with mineral medium amended with humic acids or lignocellulose. The growing fungal colonies were isolated and tested on different substrates, such as complex mixtures of hydrocarbons (petrolatum and used motor oil) and powders of different plastic polymers (PET, PP, PS, PUR, PVC). Qualitative enzymatic tests were associated with the growth tests to investigate the production of esterases, laccases, peroxidases, and proteases. These enzymes are involved in the main degradation processes of recalcitrant material, and their constitutive secretion by the examined fungal strains could have the potential to be exploited for bioremediation. More than 100 strains were isolated and tested, and several isolates with good bioremediation potential were found. In conclusion, the described screening tests are an easy and low-cost method to identify fungal strains with bioremediation potential from the soil. In addition, it is possible to tailor the screening tests for different pollutants, according to requirements, by adding other recalcitrant substances to minimal culture media.

Use of mineral oil in IVF culture systems: physico-chemical aspects, management, and safety.

The study aims to summarize current knowledge on the use of oil in embryo culture systems, with a focus on proper management of different types of oil and possible impact on culture systems. PubMed was used to search the MEDLINE database for peer-reviewed English-language original articles and reviews concerning the use of oil in embryo culture systems. Searches were performed by adopting "embryo," "culture media," "oil," and "contaminants" as main terms. The most relevant publications were assessed and discussed critically. Oils used in IVF are complex mixtures of straight-chain hydrocarbons, cyclic and aromatic hydrocarbons, and unsaturated hydrocarbons, whose precise composition influences their chemical and physical properties. Possible presence of contaminants suggests their storage at 4°C in the dark to prevent peroxidation. Washing, generally performed by manufacturers prior to commercialization, may remove trace chemical contaminants. Oils reduce evaporation from culture media at rates depending on their chemical physical properties, culture system parameters, and incubator atmosphere. Contaminants - mainly metal ion and plastic components derived from refinement processes and storage - can pass to the aqueous phase of culture systems and affect embryo development. Oils are essential components of culture systems. Their original quality and composition, storage, handling, and use can affect embryo development with significant efficiency and safety implications.

Selective molecular characterization of olefins in hydrocarbon mixtures by Ag+ complexation ESI high-resolution mass spectrometry

Molecular characterization of olefins in the complex hydrocarbon mixture is of vital importance for the various hydrocarbon upgrading processes. According to the strong interaction of Ag+ with unsaturated hydrocarbon, Ag+ complexation was adopted in this study as a tool to achieve selective olefin ionization in electrospray ionization (ESI). High-resolution mass spectrometry (HR MS) was used to characterize ionized olefin molecular composition. Various model compounds, including paraffins, naphthenes, olefins, and aromatics, were used to verify the ionization selectivity. The observed olefin carbon number distribution from Ag+ complexation ESI HR MS was in agreement with those from gas chromatography-mass spectrometry equipped with the electron impact ion source (GC-EI-MS). The proposed method can be conveniently used for direct molecular characterization of olefins in mixtures without time-consuming olefin pre-separation or chemical derivatization. Olefins in coker diesel, coal tar liquid, and Fischer-Tropsch wax were successfully analyzed by the proposed method.

Range finding test and measurement of wet weight and dry weight of Vetiveria zizanioides as an initial stage of phytoremediation of soil contaminated with used lubricants

Environmental pollution caused by the development of industry and the rapid increase in the number of vehicles currently requires restrictions on the use of lubricants. Used lubricants contain complex mixtures of hydrocarbons that adversely affect plants by creating conditions that make essential nutrients such as nitrogen and oxygen needed for plant growth unavailable and cause severe problems in soil ecosystems and the rhizosphere. The accumulation of these spills can complicate the degradation process by microorganisms in the soil. Vetiver (Vetiveria zizanioides) can grow at various levels of nutrients and insufficient abiotic conditions, so it is used in multiple studies as a hyperaccumulator plant. Preliminary research in determining the concentration of used lubricant handled by the vetiver can be determined through the Range Finding Test (RFT) stage. RFT is the stage of observing the plant's ability to maintain its life while degrading pollutants. Physical observations and laboratory analysis determine how strong the plants live in media contaminated with used lubricant pollutants. The results showed that vetiver could live in an environment contaminated with used lubricants with a concentration of up to 4% of the total mass of the media (40 ppm). Sample C2 had an average growth rate of 0.481 cm/day with a root elongation ratio of 0.333. The average dry fraction of plant leaves is 0.602 and the root is 0.372.

A novel, divergent alkane monooxygenase (alkB) clade involved in crude oil biodegradation.

Alkanes are ubiquitous in marine ecosystems and originate from diverse sources ranging from natural oil seeps to anthropogenic inputs and biogenic production by cyanobacteria. Enzymes that degrade cyanobacterial alkanes (typically C15-C17 compounds) such as the alkane monooxygenase (AlkB) are widespread, but it remains unclear whether or not AlkB variants exist that specialize in degradation of crude oil from natural or accidental spills, a much more complex mixture of long-chain hydrocarbons. In the present study, large-scale analysis of available metagenomic and genomic data from the Gulf of Mexico (GoM) oil spill revealed a novel, divergent AlkB clade recovered from genomes with no cultured representatives that was dramatically increased in abundance in crude-oil impacted ecosystems. In contrast, the AlkB clades associated with biotransformation of cyanobacterial alkanes belonged to 'canonical' or hydrocarbonoclastic clades, and based on metatranscriptomics data and compared to the novel clade, were much more weakly expressed during crude oil biodegradation in laboratory mesocosms. The absence of this divergent AlkB clade in metagenomes of uncontaminated samples from the global ocean survey but not from the GoM as well as its frequent horizontal gene transfer indicated a priming effect of the Gulf for crude oil biodegradation likely driven by natural oil seeps.

On-Line Composition Analysis of Complex Hydrocarbon Streams by Time-Resolved Fourier Transform Infrared Spectroscopy and Ion-Molecule Reaction Mass Spectrometry.

On-line composition analysis of complex hydrocarbon mixtures is highly desirable to determine the composition of process streams and to study chemical reactions in heterogeneous catalysis. Here, we show how the combination of time-resolved Fourier transform infrared spectroscopy and ion–molecule-reaction mass spectrometry (IMR-MS) can be used for compositional analysis of processed plant biomass streams. The method is based on the biomass-derived model compound 2,5-dimethylfuran and its potential catalytic conversion to valuable green aromatics, for example, benzene, toluene, and xylenes (BTX) over zeolite β. Numerous conversion products can be determined and quantified simultaneously in a temporal resolution of 4 min–1 without separation of individual compounds. The realization of this method enables us to study activity, selectivity, and changes in composition under transient reaction conditions. For example, increasing isomerization of 2,5-dimethylfuran to 2,4-dimethylfuran, 2-methyl-2-cyclopenten-1-one, and 2-methyl-2-cyclopenten-1-one is observed as the catalyst is exposed to the reactant, while BTX and olefin formation is decreasing.

Development of updated RfD and RfC values for medium carbon range aromatic and aliphatic total petroleum hydrocarbon fractions

ABSTRACT Using total petroleum hydrocarbon (TPH) measurements as a tool for assessing potential human health risks associated with exposures to petroleum products in the environment poses unique challenges, as TPH represents highly variable and complex mixtures containing hundreds of individual chemicals with wide-ranging chemical and physical properties. Current risk assessment practice generally involves analysis of environmental samples for various TPH fractions and summation of risk across those fractions. The United States Environmental Protection Agency (USEPA) derived provisional toxicity criteria for low, medium, and high carbon range aromatic and aliphatic hydrocarbon fractions over a decade ago. These criteria have been used, in whole or in part, to derive risk-based cleanup levels for TPH contamination in soil and groundwater. Herein, we evaluate and update oral and inhalation toxicity criteria for two of these fractions – medium carbon range aromatics and aliphatics – using, where applicable, newer data, updated modeling techniques, and new/alternative analyses of certain endpoints, human relevance, and uncertainty. The results of the analyses support an ~10-fold increase in the USEPA provisional reference concentration (p-RfC) values from 0.1 mg/m3 to 1 mg/m3 for both medium carbon range aromatics (different uncertainty factor) and aliphatics (new study and different judgment of toxicity data from existing study). Compared to the USEPA provisional oral reference dose (p-RfD) values for the medium carbon range aromatics and aliphatics of 0.03 mg/kg-day and 0.01 mg/kg-day, respectively, the present analyses suggest the RfD for medium carbon range aromatics could be increased >6.6-fold to 0.2 mg/kg-day (updated modeling and different uncertainty factors), and the RfD for medium carbon range aliphatics could be increased ~20-fold to 0.2 mg/kg-day (new study). These updated toxicity criteria could be used by regulatory agencies to reevaluate risk-based screening levels or by risk managers to support cleanup levels for medium carbon range aromatics and aliphatics, while still ensuring adequate health protection. Implications: Petroleum products represent complex mixtures of hydrocarbons broadly comprised of aliphatic compounds (straight-chain, branched-chain, and cyclic alkanes and alkenes) and aromatic compounds such as benzene, alkylbenzenes, and polycyclic aromatic hydrocarbons. The complex nature of petroleum products presents challenges for assessing potential health risks associated with exposure to petroleum hydrocarbon contamination in the environment. It has been over ten years since the U.S. Environmental Protection Agency derived provisional toxicity criteria for low, medium, and high carbon range aromatic and aliphatic hydrocarbon fractions. In that time, risk assessment guidance and tools have evolved, and new studies have been published. Our analyses indicate that current provisional toxicity criteria for medium carbon range aromatics and aliphatics fractions are overly conservative by approximately an order of magnitude.

Petroleum rock mechanics: An area worthy of focus in geo-energy research

Petroleum rock mechanics: An area worthy of focus in geo-energy research

Gas Chromatography-Atmospheric Pressure Inlet-Mass Spectrometer Utilizing Plasma-Based Soft Ionization for the Analysis of Saturated, Aliphatic Hydrocarbons.

Soft ionization by a chemical reaction in transfer (SICRIT) is applied to couple gas chromatography (GC) to a high-resolution atmospheric pressure inlet mass spectrometer. These instruments are generally used in combination with liquid chromatography systems (LC-MS). Ionization of alkanes is not possible here with conventional electrospray ionization. Alternatively, separate GC-electron ionization (EI)-MS is employed for the analysis of nonpolar substances like alkanes, however, with the inherent challenge of strong fragmentation. In the case of alkanes, the determination of molecular masses becomes nearly impossible in complex hydrocarbon mixtures because of the wealth of similar fragment ions and the absence of the molecular ion signal. SICRIT, a soft ionization technique based on dielectric barrier discharge (DBDI), produces characteristic oxidized cations from alkanes that can be directly correlated to their molecular mass. Isotope labeling experiments reveal an ionization mechanism via hydride abstraction and reaction with water. Soft ionization can be achieved for iso- and n-alkanes, with very little fragmentation, enabling the determination of their molecular mass. Calibrations for n-alkanes from C10 to C30 were performed exhibiting high linearity, reproducibility, and sensitivity with an average LOD of 69 pg (on column). Measurements of diesel fuel samples are compared to traditional GC-EI-MS. The presented method combines sensitivity and easy handling of a GC-EI-MS with the determination of molecular mass commonly only achieved with field ionization (FI)-MS, while using existing and highly optimized mass spectrometers commonly coupled with LC. Additionally, many other analytes such as (alkylated-) PAHs could be detected simultaneously in the diesel sample.

Multivariate statistics for summarizing diesel feeds for flammability attributes using comprehensive two-dimensional gas chromatography.

Comprehensive 2D gas chromatography has been utilized for analyzing complex mixtures of hydrocarbons of diesel feeds. Here, we evaluated 19 diesel feeds for their paraffinic, naphthenic, and aromatic group compositions dictating their flammability properties. Compositional ranges of feeds were as follows: paraffins: 9.6-57.8%, naphthenes: 7.9-38.5%, and aromatics: 10.5-82.3%. Diesel's flammability performance is estimated by thermodynamic conditions and rates of radical formation of hydrocarbon type in actual engine condition, limiting cetane number. However, limitations are overcome by understanding the relative compositional variations of feeds by simple ranking of feeds based on C15-16 compositions. Due to the multidimensional variability of feeds, a principal component analysis was adopted later for its distinguishing capability. Paraffinic, naphthenic, and aromatic group's principal component analysis clustered up feeds based on the higher concentration of individual hydrocarbon group. We explored hierarchical cluster analysis to organize feeds into classes of mixed C9 to C26 paraffin's composition in the diesel range. Further, for discriminating C15-C16 enriched and depleted feeds in total paraffin composition, a row dendrogram with heat map was drawn. The above multivariate methods have led to a fair distinction of nonadditive feed compositions influencing flammability properties by radical formation rate.