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Highlights • Petroleomic was applied to 69 off-shore Brazilian crude oils samples. • Kerogen type plays an important control on NSO compounds. • Clear separation based on polar species found in marine and lacustrine oils. • Negative ESI FTICR-MS can be used to perform geochemical assessment in crude oils. Abstract Lacustrine and marine crude oils from different off-shore Brazilian basins were analyzed using a 7.2 Tesla LTQ FTICR-MS instrument. The samples were analyzed via electrospray ionization in the negative ion mode focusing on the polar compounds, i.e., nitrogen-, sulfur-, and oxygen-containing (NSO) compounds. We also employed a combination of other geochemical methods, such as GC-FID and GC-MS analyses, to characterize and assess the depositional environments of the different oil families. The results indicate that lacustrine oils tend to be enriched in Nx compounds, while marine oils show preference for Ox compounds. The dominant heteroatomic classes in crude oils are N1, followed by O1, O2, and N1O1 with remarkable differences in their distributions between marine and lacustrine, strongly suggesting the control by the kerogen type of the heteroatomic compounds found in these crude oils. Considerable differences in the DBE distribution of the main classes analyzed between the crude oils allowed an efficient geochemical characterization regarding their origin. The use of negative ESI FTICR-MS as a geochemistry tool can provide additional information beyond that obtained with currently employed geochemical methods, resulting in the full comprehension of crude oil composition. [ABSTRACT FROM AUTHOR]

The thermal maturity level impact on polar compounds was analyzed for a suite of hydrous pyrolysis (HP) products using a 7.2 Tesla LTQ FTICR-MS instrument. The sample suite was analyzed via electrospray ionization in the negative ion mode focusing on the polar compounds, i.e., nitrogen-, sulfur-, and oxygen-containing (NSO) compounds. The HP experiments were performed under isothermal conditions for 2 h at eleven different temperatures (300, 310, 320, 325, 330, 340, 345, 350, 355, 360 and 365 °C) to simulate the full range of thermal levels starting at early bitumen generation to maximum oil generation. The maturity suite samples consist of one immature bitumen (original sample), eleven expelled oil samples and eight residual bitumen samples. In general, O x compounds are destroyed by decarboxylation and dehydration with increasing maturity; sulfur compounds decrease; the aromaticity and degree of condensation increase; and steranoic and hopanoic acids decrease. Additionally, we investigated fluid retention properties comparing the carbon number distribution between the expelled oil and residual bitumen samples from each experiment. The maturity related changes of the acidic O 2 compounds in the expelled oil samples led us to create several regressions that we propose as new maturity parameters covering the full range of oil generation. [ABSTRACT FROM AUTHOR]

This study extends the analysis of previously well studied biodegraded crude oil case history sample sets. The analytical window is extended into the high molecular weight, aromatic hydrocarbon and non-hydrocarbon fraction of crude oils, using a 12 T ultra-high resolution mass spectrometer (FTICR-MS). Biodegradation is pervasive across compound groups and extent of degradation appears dependent on compound abundance and hence availability. Oil constituents with molecular weights up to m/z 600 (carbon number 44) are affected by in-reservoir biodegradation. Apart from special, specific compound groups possibly related to the active reservoir biomass, all hydrocarbon and single heteroatom-containing compound classes are depleted by biodegradation. Production of various highly alkylated species indicate that transformation of crude oil components often involves derivatization and preservation rather than just complete destruction of high molecular weight compounds. Whereas one case study shows good correlation between depletion of S1 species and a strong increase in SO2 species, a nitrogen enriched oil suite shows an analogous trend in the transformation of N1 species to the corresponding NO2 species. Increase in O2 species are seen in both sample sets indicating partial oxidation is a major overall process in in-situ reservoir biodegradation. These variations are important geochemically but also impact transport, interfacial and corrosion properties of oils. Nitrogen isotope systematics indicate that nitrogen-containing compounds might act as nitrogen nutrient sources or mainly as carbon sources for the microorganisms causing in-situ reservoir biodegradation depending level of biodegradation. Distributions of some heterocyclic species add a very biodegradation resistant parameter set, to the petroleum geochemists arsenal. [ABSTRACT FROM AUTHOR]

Reactive oxygen species (ROS) are thought to play an important, although poorly understood, role in modifying the composition of terrigenous-derived dissolved organic matter (tDOM) upon export to aquatic systems. Of the dominant ROS in natural systems, OH has been shown to substantially modify lignin under laboratory conditions, simulating processes responsible for transformation of DOM in natural waters. Utilizing high performance liquid chromatography (HPLC) in conjunction with ultrahigh resolution mass spectrometry, we examined HPLC fractionated lignin extracts in an effort to establish which fractionated components of the lignin extract were (i) most susceptible to attack by OH and (ii) most likely to be responsible for compounds observed in the DOM. The results indicate that the most polar components of the lignin extract, representing tDOM, could be responsible for a large portion of newly generated formulas observed within DOM in natural waters. This suggests that partially oxidized lignin may be readily altered to compounds observed in DOM which are not typically associated with terrigenous OM, such as alicyclic and condensed aromatic-like compounds. [ABSTRACT FROM AUTHOR]

Molecular composition of surface sediments reflects a shift in the nature of organic matter along the land-sea transect in the Pearl River estuary and coastal South China Sea. [Display omitted] • Comprehensive molecular screening of organic matter in surface sediment from land to sea. • Freshwater site is characterized by hydrocarbon and sulfur-containing compound classes. • Marine site shows molecular indicators of phototroph sourced biomass. • FTICR-MS rapidly characterized dynamic changes of organic matter along environmental gradients. 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 used a newly developed single injection Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) method to analyze organic extracts of surface sediments transitioning from freshwater to marine settings in the Pearl River estuary and coastal South China Sea. Results show a complex mixture of molecular markers, with distinct fingerprints characterizing the freshwater and saline sites. Notable examples include steroidal and thiophenic species at the freshwater site, indicative of possible anthropogenic organic matter inputs from the continent; on the other hand, samples from the coastal site are uniquely characterized by putative tetrapyrrole species, indicative of phaeopigments sourced from marine phytoplankton. This study demonstrates the potential application of single injection FTICR-MS in rapidly probing the dynamic changes of organic matter sources and fates occurring in estuaries influenced by anthropogenic activities. [ABSTRACT FROM AUTHOR]

Exposure of lignin-derived organic matter (OM) to hydroxyl radicals originating from Fenton type reactions generates condensed aromatic and alicyclic aliphatic compounds, as shown using ultrahigh resolution mass spectrometry. Although condensed aromatic compounds are common in soil and dissolved OM, their presence has been attributed largely to combustion. A non-pyrogenic route for the formation of condensed aromatic compounds from lignin is suggested here, specifically that hydroxyl radical-initiated oxidation of lignin is capable of producing black carbon-like condensed aromatic compounds. Alicyclic aliphatic compounds are also produced, likely as part of a concerted process involving ring opening, polymerization and/or cyclization and hydrogen abstraction. Hydroxyl radicals associated with lignin degradation are produced through photochemistry in aqueous systems and enzymatic microbial processes in soil. [ABSTRACT FROM AUTHOR]

We have examined, using a 12 Tesla FTICR-MS instrument, the impact of varying thermal maturity level on a suite of 9 related crude oils charged from source rocks covering most of the liquid petroleum generating portion of the oil window (0.68–1.11% vitrinite reflectance equivalent (%Re)). The sample suite was analyzed as whole oils under three different conditions, electrospray ionization (ESI) in positive and negative ion mode to analyze basic and acidic components, respectively, and atmospheric pressure photoionization (APPI) in positive ion mode, for sulfur and hydrocarbon species. Increasing oil maturity level had a strong influence on the composition of all compound classes in the oils with several major observations evident: The relative apparent abundances of all heteroatom containing compound classes detected in this study, using all ionization modes, decrease systematically with increasing oil maturation levels. Both aromatic hydrocarbons, detectable in APPI mode, and NSO compound classes (detectable in both ESI and APPI modes), as broad classes, are becoming more aromatic (shift to a greater predominance of higher DBE group members) and dealkylated (decreasing average molecular mass of individual compound groups), with increasing maturation level in the oil suite. Several putative oil maturity level dependent, molecular ratios were identified in the study. Of particular note, the relative abundance ratios of heteroatom compound classes tentatively identified as alkylated carbazoles, quinolines and benzothiophenes, compared to their benzannulated homologues are very sensitive to maturation level. Several groups of compounds show interesting and specific carbon number distributions, suggesting there may be hints of specific molecular markers in the FTICR-MS data. One observation of note is the strong increase in the relative abundance of protonated hydrocarbon components with DBE 5. We speculate this might reflect the presence of previously unreported higher molecular weight diamondoid (diamantane) species in oils with up to 40 carbon atoms or more, at advanced maturity levels. Such species may prove very valuable as molecular markers in highly mature fluids, such as those currently being produced from some shale reservoirs. Covariation of quantitative GC–MS data for alkylated hetero aromatic sulfur and nitrogen compounds in this oil suite, together with the corresponding FTICR-MS data from compounds believed to be, based on accurate mass, alkylated sulfur and alkylated nitrogen compounds, suggests that FTICR-MS already has some very rudimentary quantitation capabilities. [ABSTRACT FROM AUTHOR]

• Oils from carbonate and siliciclastic rocks can be distinguished by composition. • The differences are more pronounced in the O 1 , N 1 S 1 , S 1 and HC species. • Two novel source-related proxies based on FTICR–MS data are identified. • Published FTICR–MS data were used to verify the robustness of the proposed proxies. The scope of this study was to develop robust lithofacies proxies which are less affected by other geochemical processes such as maturity and biodegradation. Here, crude oils derived from carbonate and siliciclastic source rocks from different petroleum settings were investigated using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), thereby providing information on the role of depositional environment in controlling the chemical composition of hydrocarbons. The carbonate oils belong to the Western Canada Sedimentary Basin (WCSB) and the siliciclastic oils were mainly collected from the Austrian parts of the Molasse Basin and the Vienna Basin, Austria. The variations in chemical composition, aromaticity as well as alkylation degree of the main compound classes in both oil types are discussed in detail using data from FTICR-MS in two different ionization modes: electrospray ionization in negative ion mode (ESI–N) and atmospheric pressure photoionization in positive ion mode (APPI–P). The results obtained from both ionization modes indicate that the chemical compound distributions of acidic constituents such as oxygen-only components (the O 1 to O 4 classes) and the N 1 S 1 class, as well as sulfur and hydrocarbon species in oils from carbonates are clearly different from those generated by siliciclastic rocks. Most likely, the observed differences are attributed to depositional environments of the respective source rocks as the impacts of other processes such as thermal maturity and biodegradation, were mitigated by selection of non-biodegraded oils that display comparable maturation levels. The calculated vitrinite reflectance (%R c) in most of the selected oils range between 0.5 and 0.8. The observed differences in chemical composition of oils from carbonates and siliciclastics lead to suggested novel source-sensitive proxies based on the DBE distribution of the S 1 and HC species (from APPI–P) and the O 1 and N 1 S 1 classes (from ESI–N). The former proxy is the ratio of the S 1 class DBE 9 group (radical ions; likely sum of alkylated dibenzothiophenes) relative to the HC class DBE 10 group (radical ions; likely sum of alkylated phenanthrenes). It appears that this proxy is mirroring the "DBT/P ratio" obtained from GC–MS data over a much broader range of molecular masses up to approximately 1000 Da. The other proxy is based on the observed differences between the O 1 class DBE 4 group and the N 1 S 1 class DBE 14 group. Whereas oils derived from the siliciclastic source rocks show higher concentrations of the O 1 class, oils originated from the carbonate source units are enriched in the N 1 S 1 species. Finally, published FTICR-MS data (APPI–P) from both oil source types with varying levels of maturation and biodegradation are included, in order to verify the robustness of the proposed proxies. [ABSTRACT FROM AUTHOR]

• Oils with higher saturated hydrocarbon content are more prone to alteration by radiolysis. • Evidence suggests radiolysis-induced polymerization. • New hydrocarbon species with no or low aromaticity form. • Oxygenated species are plausible candidates for radiolysis proxies. • Carbon-carbon double bonds are the most promising radiolysis proxy. Natural nuclear radiation-induced alteration of subsurface fluid composition has been recently proposed as a geochemical tool for petroleum system analysis. This paper describes how gamma radiation (doses up to 4000 kGy) affects the composition of crude oil based on ultrahigh-resolution mass spectrometry and nuclear magnetic resonance (NMR). Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) with electrospray (ESI) and atmospheric pressure photoionization (APPI) ion sources are used to target polar, high molecular-weight and/or heteroatom-containing species, whereas NMR analysis targets carbon-carbon double bonds generated by radiolysis. Oils with lower density and higher saturated hydrocarbon content are more susceptible to radiolysis, and the presence of water is confirmed to cause formation of O-bearing organic compounds. Preliminary evidence indicates radiolysis-induced polymerization reactions, as well as the decreased amounts of S- and N-bearing species with increased radiation dose. Hydrocarbon species with no or low aromaticity form within the oil matrix. Carbon-carbon double bonds likely facilitate the detection of such compounds in ESI and APPI modes. Oxygenated species with low aromaticity arising from the reaction of oil matrix compounds with water-derived, radiolysis-generated reactive oxygen species are also suitable candidates for future radiolysis proxies. NMR confirms the occurrence of carbon-carbon double bonds produced during radiolysis and was used to calibrate their concentration vs. the radiation dose. Preliminary FTICR-MS-based radiation proxies have been proposed, and their implications assessed. However, we acknowledge further analytical development is needed. [ABSTRACT FROM AUTHOR]

• Pyrogenic dissolved organic matter (Py-DOM) is molecularly heterogeneous. • Complementary analyses are needed to representatively characterize Py-DOM composition. • Py-DOM becomes less oxygenated, more aromatic, and more aliphatic with increasing char maturity. • Grass and oak pyrolyzed via similar conditions vary in char maturity and likely environmental fate. Pyrogenic organic matter (Py-OM), generated via the incomplete combustion of biomass, is well studied due to the presence of slow-cycling, condensed aromatic compounds (ConAC) known to sequester in soils and sediments. Recently, dissolved Py-OM (Py-DOM) has received interest, due to its higher mobility and potential to be transferred through watersheds to aquatic systems. Py-DOM quantities, molecular identities and importance to global carbon budgets and cycles are only beginning to be understood. Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) analyses were performed on Py-DOM isolated from oak and grass biochars produced over a range of temperatures (250–650 °C), and the data are compared to complementary 1H NMR spectroscopic and benzenepolycarboxylic acid biomarker (BPCAs) analyses. Py-DOM is revealed to be a heterogeneous mixture of compounds ranging in relative aromaticity and oxygenation. FTICR-MS analyses demonstrate a decrease in Py-DOM relative oxygen content and a concurrent increase in aliphatic character and heteroatomic (N, Cl) content. 1H NMR and BPCAs analyses detail low O/C dissolved ConAC not observed by FTICR-MS, demonstrating the necessity for a multiple proxy approach to Py-DOM characterization. Heterogeneous Py-DOM is explained as resulting from pyrolysis-initiated and radical-mediated functional group cleavage, aromatic condensation and aromatic ring-opening reactions. Oak biomass progresses faster along a char maturity continuum for a given pyrolysis temperature, perhaps due to its greater lignin content or radical quenching by grass cuticular material. Biomass species and pyrolysis temperature likely result in different Py-DOM compositions and fates and must be considered when evaluating the impacts of wildfires and biochar applications. [ABSTRACT FROM AUTHOR]

• Lipids with ≤6 S atoms have been detected as free molecules in sulfur rich oils. • Immature sulfur rich oils contain S-steroids, -hopanoids, -carotenoids, -alkenones. • (+) APPI CID-FTICR-MS indicated only minor thiols and sulfide bridges. • Precursor and sulfurized products relationships are clarified. • Some geoengineering paths to carbon sequestration require such understanding. Sulfur incorporation into sedimentary organic matter has a key role in carbon preservation in the geosphere. Such processes can inform strategies for human timescale carbon storage to mitigate climate change impacts and thus more detailed knowledge of sulfur incorporation into biomass species is needed. Until recently, detailed chemical characterization of sulfurized organic matter was only possible by analyzing individual building blocks obtained after desulfurization reactions. In this study, Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), with atmospheric pressure photoionization in positive ion mode, (+) APPI, was used to investigate the chemical composition of sulfur rich crude oils and to obtain mechanistic insights into the sulfur incorporation reactions happening during early diagenesis. Contrary to expectations, (+) APPI FTICR-MS data show that sulfurized lipids (with up to 6 sulfur atoms and up to m / z 1100) occur as free molecules in these oils, rather than within a macromolecular network linked by (poly)sulfide bridges. In contrast to the mature Peace River (Canada) oils, the thermally immature Rozel Point (USA) and Jianghan Basin (China) oils show a carbon number preference in sulfurized species resembling biogenic precursor molecules, which highlights the importance of S-bound molecules as geochemical proxies for early diagenetic processes. This study indicates that sulfur incorporation reactions involve the formation of S-cyclic structures in which the double bond equivalent is ≥ the number of S atoms. Collision induced dissociation (CID-) FTICR-MS experiments suggest the occurrence of intermolecular sulfur incorporation reactions, but only as a mechanism that is secondary to intramolecular sulfur addition. The CID-FTICR-MS experiments indicated that steroid sulfurization typically yields S-bearing cyclic structures and that thiol/thioether groups may be present throughout the chemical matrix but only to a minor extent. In addition, CID-FTICR-MS also confirms the occurrence of sulfurized alkenones in low maturity oils. Knowledge of organic sulfur molecule formation informs routes for carbon dioxide removal technologies that could be used to sequester carbon in the geosphere and/or hydrosphere in the form of recalcitrant organic species. [ABSTRACT FROM AUTHOR]

• A relationship exists between SOC content and the composition of soil HAs. • Unsaturated lipid and lignin structures prevail in high SOC content scenarios. • Saturated lipid prevails in low SOC content scenarios. • Humic acid structure keeps information on soil properties as SOC content. • The SOC can be predicted from the molecular composition of HAs. Long-term stabilization of soil organic matter (SOM) plays an important role in the carbon cycle. Hence, understanding biogeochemical mechanisms of soil C sequestration is crucial to control its release to the atmosphere. This study aims at investigating the biogeochemical mechanisms of soil C sequestration. An exploratory assessment was carried out on the information about the soil C levels provided by the molecular composition of humic acids (HAs) analyzed by electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Significant PLS forecasting model for total soil C was obtained using as descriptors the 131 compounds in common in all the HAs detected by FTICR-MS, and its variable importance for projection (VIP) was plotted in the space defined by their atomic ratios using van Krevelen diagrams. The results indicated that significant relationship exists between the HAs molecular composition and the soil organic C levels. The VIP values for the different groups of compounds illustrate how HA contains information about the amounts of C stored in the soil: the HAs in the soils with high levels of organic C have significantly (P < 0.1) higher proportions of unsaturated lipid and lignin-derived compounds; on the other side, low soil organic C levels are associated to HAs with comparatively high proportions of saturated lipid compounds. [ABSTRACT FROM AUTHOR]

• Water-soluble petrogenic and pyrogenic organics were characterized using FTICR-MS. • Burning oil introduces oxidized and highly unsaturated organics into the water. • ISB greatly increases concentration of organics partitioning into the water phase. In situ burning is often used as a response method for oil slicks in the marine environment. This process however forms viscous tar-like residues that either float on the surface or sink through the water column, introducing organic species into the water phase. The interaction of this burn residue with the water phase also introduces dissolved organics into the water column. In this study, we conducted laboratory-scale experiments to characterize and compare the organic species entering the water phase from the petrogenic (fresh oil) and pyrogenic (burnt oil) input during oil spills. The oil and water-soluble organics were characterized using ultra-high-resolution mass spectrometry (FTICR-MS). The results show that burning strongly increases concentrations of oil-related constituents entering the water phase, due to transformation reactions producing oxidized organic species with higher water solubility. The pyrogenic water-soluble organics also showed a higher percentage of unsaturated compounds relative to the petrogenic fraction. The effect of these highly unsaturated and oxygenated organic species on oil spill fate and their ecosystem impacts is currently unknown. [ABSTRACT FROM AUTHOR]