Mechanistic insights into sulfur rich oil formation, relevant to geological carbon storage routes. A study using (+) APPI FTICR-MS analysis

Silva, Renzo C.; Yim, Calista; Radović, Jagoš R.; Brown, Melisa; Weerawardhena, Priyanthi; Huang, Haiping; Snowdon, Lloyd R.; Oldenburg, Thomas B. P.; Larter, Steve

doi:10.1016/j.orggeochem.2020.104067

Cited by 14 publications

(11 citation statements)

References 59 publications

(98 reference statements)

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“…Subsequently, low-carbon number/oxidized photoactivated species undergo polymerization and produce heavily oxidized compounds with higher carbon number and higher DBE. Additional experimental evidence for the existence of polymerization in asphaltenes is needed and should address the possible occurrence of addition reactions between sulfide moieties (R–S–R′) for sulfur-enriched oils such as Athabasca bitumen and South American crudes, as previously shown in the geochemistry studies by Silva et al …”

Section: Resultsmentioning

confidence: 91%

Role of Molecular Structure in the Production of Water-Soluble Species by Photo-oxidation of Petroleum

Chacón-Patiño

Niles

Marshall

et al. 2020

Environ. Sci. Technol.

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Asphaltenes are high-boiling and recalcitrant compounds that are generally minor components of crude oil (∼0.1–15.0 wt %) but dominate the composition of heavily weathered spilled petroleum. These solid residues exhibit a high structural complexity, comprised of polycyclic aromatic hydrocarbons (PAHs) that are a mixture of single-core (island) and multicore (archipelago) structural motifs. The mass fraction of each motif is sample-dependent. Thus, knowledge of a potential structural dependence (single- versus multicore) on the production of water-soluble species from asphaltene samples is key to understanding the contribution of photochemically generated dissolved organic matter from oil spills. In this work, asphaltene samples with enriched mass fractions of either island (single-core) or archipelago (multicore) structural motifs are photo-oxidized on artificial seawater by the use of a solar simulator. Molecular characterization of oil- and water-soluble photoproducts, conducted by Fourier transform ion cyclotron resonance mass spectrometry, reveals that island motifs exhibit very limited production of water-soluble species, and their oil-soluble products reflect the molecular composition of the starting material. Conversely, archipelago motifs yield a water-soluble compositional continuum of O x , S x O y , and N x O y containing hydrocarbons species that exhibit the typical molecular fingerprint of dissolved organic matter (DOM). The lower carbon number and aromaticity of the archipelago-derived asphaltene photoproducts suggest the occurrence of photofragmentation (or photolysis) reactions. To investigate the possibility of the opposite reaction (photopolymerization), the photo-oxidation of small PAHs isolated from a low-boiling petroleum distillation cut was also performed. It yielded water-soluble compounds with carbon number and aromaticity up to 2-fold higher than the starting material, strongly suggesting that polymerization (addition reactions) occurs. Collectively, the results indicate that the presence of archipelago motifs and the occurrence of cracking/polymerization reactions are central in the production of dissolved organic matter from fossil fuels.

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Section: Resultsmentioning

confidence: 91%

Role of Molecular Structure in the Production of Water-Soluble Species by Photo-oxidation of Petroleum

Chacón-Patiño

Niles

Marshall

et al. 2020

Environ. Sci. Technol.

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“…35 This "smoothing-out" of geochemical fingerprints is what is typically observed in crude oil samples, where the original fingerprint of source fossil organic matter is made uniform by catagenetic processes occurring over geological timescales. [36][37][38][39] However, in the case of sediments analyzed in this study there is a very pronounced preference in carbon distributions of the molecular markers detected, characteristic of relatively recently deposited organic matter found in modern sedimentary environments, 40 as exemplified herein by the odd-to-even, C31-35 carbon sequence within the DBE 2 group of O2 compound class. Therefore, possibly a more plausible identity of these species would be long chain di-ketones, i.e., diones, analogs of well known alkenones, and related to C31, C33, and C35 species in the DBE 1 group of compound class O (as discussed above).…”

Section: Oxygen-containing Compound Classesmentioning

confidence: 54%

“…We have previously reported C40 species in both recent sediments and immature crude oils and related them to carotenoid pigments. 7,39 We hypothesize that the C40 species detected in this study may also be related to carotenoids and their alkylated derivatives.…”

Section: Oxygen-containing Compound Classesmentioning

confidence: 70%

Multi-proxy assessment of surface sediments using APPI-P FTICR-MS reveals a complex biogeochemical record along a salinity gradient in the Pearl River estuary and coastal South China Sea

Radović¹,

Xie²,

Silva³

et al. 2021

Preprint

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The Pearl River drains the second largest watershed in China, funnelling large amounts of freshwater and organic matter into the northern part of the South China Sea through an estuary characterized by pronounced biogeochemical gradients. In this study we analyzed organic extracts of surface sediments collected along land-sea transect that captures a transition from freshwater environment at the site of the Pearl River discharge, to marine settings at the most distal sampling point in the coastal South China Sea. Samples were analyzed using Fourier transform ion cyclotron mass spectrometry (FTICR-MS), to assess the molecular composition of the organic species present in the sediment and understand the sources and diagenesis of deposited organic matter. Results show a complex mixture of molecular markers, many of which can be used as proxies to distinguish between the freshwater and saline settings. For example, geochemical signal at the freshwater site is notably characterized by species belonging to hydrocarbon and sulphur-containing compound classes – these are likely markers of terrestrial, natural and/or anthropogenic organic matter inputs. On the other hand, samples from the coastal marine site bear a unique signature of putative tetrapyrrole species, molecular indicators of phytoplankton phaeopigments. Notably, some unusual and or novel species, such as sterenes and alkanones were putatively identified. These and other biomarkers species that can be detect using our single injection method provide convenient multiple proxies necessary for interpreting dynamic changes from land to the ocean, which have even been complicated by anthropogenic activities.

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“…High-resolution mass spectrometry, such as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), provides ultrahigh mass resolution and mass accuracy to reliably calculate the molecular elemental composition on the basis of molecular mass. In the past two decades, the application of high-resolution mass spectrometry has enabled the molecular compositional characterization of sulfur compounds in the whole petroleum and its products. ,− …”

Section: Characterization Techniquesmentioning

confidence: 99%

“…Silva et al investigated the chemical composition of sulfur-rich crude oils via FT-ICR MS. Sulfurized lipids (with up to 6 sulfur atoms and up to m / z 1100) are found as free molecules in the oils rather than within a macromolecular network linked by sulfide bridges. Intermolecular sulfur incorporation is not the major mechanism to intramolecular sulfur addition.…”

Section: Geological Formation Of Sulfur Compoundsmentioning

confidence: 99%

Review on Sulfur Compounds in Petroleum and Its Products: State-of-the-Art and Perspectives

Shi

2021

Energy Fuels

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Sulfur compounds have significant geochemical information, and the removal of sulfur from petroleum products is one of the most important tasks in petroleum refining. However, it is a challenging task to reveal the chemical composition of sulfide at the molecular level because of its complex composition. Unremitting efforts have been made to develop methods for the separation and characterization of sulfur compounds in petroleum and its products in order to understand the mechanisms of their geological origin and their transformation in petroleum processing. Sulfur compounds include thiophenes, sulfides, thiols, sulfoxides, and sulfones, etc. The sulfur element is mainly from sulfate in the sedimentary environment, but the combination of sulfur into hydrocarbons could occur in different ways. Most sulfur compounds are generated in the early diagenetic period through the reaction of unsaturated organic matter with H2S or elemental sulfur released from sulfate via bacterial sulfate reduction. The composition of the sulfur compound in petroleum could be largely altered by thermal maturation, leading to an increase in the relative abundance of highly condensed aromatic sulfur compounds. Another important pathway of sulfur addition is thermochemical reactions between sulfate and hydrocarbons at high temperatures. Some sulfur compounds have a relatively weak chemical stability and are easily decomposed into small-molecule sulfur compounds in petroleum processing. Removing sulfur from petroleum is an essential task for petroleum refinement and upgrading, in which the steric hindrance effect is the most important factor affecting the desulfurization activity of sulfur compounds via hydrotreating. Some polar sulfur compounds are difficult to hydrogenate to remove sulfur; however, the chemical structures of these compounds are unclear. High-resolution mass spectrometry has revealed the high complexity of the molecular composition of sulfur compounds in heavy oils and their polar fractions. However, understanding of their molecular structure is limited, and further research should focus on the formation and transformation mechanism of these polar sulfur compounds. This review will focus on the molecular composition of petroleum sulfur compounds with a collection of topics of sulfur compounds that covers the upstream and downstream petroleum industry, including separation and characterization methods, molecular and structural composition of various sulfur compounds, mechanisms of their geological origin, and their transformation during petroleum processing.

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Mechanistic insights into sulfur rich oil formation, relevant to geological carbon storage routes. A study using (+) APPI FTICR-MS analysis

Cited by 14 publications

References 59 publications

Role of Molecular Structure in the Production of Water-Soluble Species by Photo-oxidation of Petroleum

Role of Molecular Structure in the Production of Water-Soluble Species by Photo-oxidation of Petroleum

Multi-proxy assessment of surface sediments using APPI-P FTICR-MS reveals a complex biogeochemical record along a salinity gradient in the Pearl River estuary and coastal South China Sea

Review on Sulfur Compounds in Petroleum and Its Products: State-of-the-Art and Perspectives

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