Occurrence, distribution and sources of petroleum contamination in reef-associated sediments of the Gulf of Mannar, India.

The distribution of saturated hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) was assessed in superficial sediment samples collected from Mandapam island groups, Gulf of Mannar, India. The hydrocarbon distribution pattern and the n-alkane indices (e.g., carbon preference index (CPI) and natural n-alkanes ratio (NAR)) were deployed to differentiate between the biogenic and anthropogenic sources. Petroleum pollution was indicated by the pristane/phytane ratio close to 1. Presence of a prominent unresolved complex mixture (UCM) as well as hopane concentrations further supported this assertion. The evaluation of petrogenic sources of contamination were also comprehended by various diagnostic ratios of PAHs. The sites associated with shipping activities, tourism, and located near the mainland and accessible portions of the islands exhibited high petroleum contamination. Correlation analysis underlines the significance of combining petroleum-specific marker compounds and diagnostic ratios to improve the assessment of human influence on marine ecosystems.

A small-scale neutral alumina column chromatography method for carbon isotope determination of hopanes in crude oils or rock extracts.

This paper presents a small-scale column chromatography method for separating hopanes in crude oil or rock extracts using neutral alumina as a solid phase adsorbent and a Pasteur pipette as a separation device. Three oil samples were selected to study the effect of solid phase adsorbent type and column length on the separation of hopanes. The oil samples were eluted with mixed reagents (V hexane: V petroleum ether = 8:2) and collected at intervals of 0.5 ml. Ten Fractions were collected and tested for the compounds using GC-MS. A quantitative approach was used to reveal distribution characteristics of compounds in each eluted Fraction. Experimental results showed that 100-200 um neutral alumina exhibited significant differences in the adsorptive capacity of biomarkers from oil samples and rock extracts. The elution order of the biomarkers in the chromatographic column (the length is 180 mm) was n-alkanes, steranes and hopanes. The separation of hopanes could be realized by collecting the eluted Fractions 4 and 5. Compared with the urea complexation, the purity of hopanes separated by column chromatography was higher. The concentration of n-alkanes (nC16-nC34) could be reduced from 1.99 to 4.83 mg/ml to 0.79-0.94 mg/ml, and the content of steranes can be reduced from the original 12% to 0.45%. Residual n-alkanes and steranes were not visible in the GC-MS detection. The Total Ion Chromatography (TIC) of hopanes was consistent with the distribution characteristics of the m/z191 mass chromatogram. The isolated hopanes could meet the detection requirements of isotope ratio mass spectrometry. The C29Ts/C29αß ratio of hopanes decreased gradually from 1.63 to 0.73 as the column length increased. It is speculated that the variation of the C29Ts/C29αß ratio is not only affected by maturity but also by the oil and gas migration. This method is a new attempt in the field of compound purification and can be widely used in the study of stable carbon isotopes of hopanes monomeric hydrocarbons.

The fingerprint stability of the biomarker hopanes and steranes in soot emissions from in-situ burning of oil.

The behavior of emissions is an important concern of in-situ burning (ISB) of spilled oils. In particular, the heavy soot originated from ISB can negatively impact the atmospheric environment. To track the behavior of ISB soot, the conservative biomarkers, such as hopanes and steranes, can be potentially used. In this study, the stability of chemical fingerprints of hopanes and steranes in the ISB soot were investigated based on the burning of two different types of oils, including one ultra-light condensate (i.e., surrogate Sanchi condensate) and one heavy oil. The results indicate that the chromatographic patterns and diagnostic ratios of hopanes and steranes in the ISB soot emissions almost remain identical to their corresponding source oils, proving the various oil source identification of ISB soot can be realized. This work attempts to provide novel insights into the application of biomarkers in the management of ISB emissions.

Environmental fate of petroleum biomarkers in Deepwater Horizon oil spill residues over the past 10 years.

The long-term fate of three groups of petroleum biomarker compounds (terpanes, steranes, and triaromatic steranes) was investigated in the Deepwater Horizon (DWH) oil spill residues collected from Alabama (USA) beaches over the past 10 years. This is the first study to investigate the long-term fate of these three groups of petroleum biomarkers in DWH oil spill samples over 10 years. We employed the highly recalcitrant C30 αß-hopane as an internal biomarker to quantify the degradation levels of different biomarker compounds, and also to estimate the overall weathering levels of DWH oil spill residues. The data show that four lower molecular weight tricyclic terpanes (TR21, TR22, TR23, and TR24), three lower molecular weight steranes (S21, S22, and C27), and all triaromatic steranes degraded over the 10-year study period. All other terpanes (including hopanes) and steranes remained recalcitrant. There have been contradicting literature data on the degradation levels of homohopanes, and this field study demonstrates that all the homohopanes remained recalcitrant after 10 years of natural weathering. Our data also show that despite some degradation, the relative diagnostic ratios of the biomarkers remained stable for all three groups of biomarkers over the 10-year period.

Pulque production from fermented agave sap as a dietary supplement in Prehispanic Mesoamerica.

Although in modern societies fermented beverages are associated with socializing, celebration, and ritual, in ancient times they were also importa`nt sources of essential nutrients and potable water. In Mesoamerica, pulque, an alcoholic beverage produced from the fermented sap of several species of maguey plants (Agavaceae; Fig. 1) is hypothesized to have been used as a dietary supplement and risk-buffering food in ancient Teotihuacan (150 B.C. to A.D. 650). Although direct archaeological evidence of pulque production is lacking, organic residue analysis of pottery vessels offers a new avenue of investigation. However, the chemical components of alcoholic beverages are water-soluble, greatly limiting their survival over archaeological timescales compared with hydrophobic lipids widely preserved in food residues. Hence, we apply a novel lipid biomarker approach that considers detection of bacteriohopanoids derived from the ethanol-producing bacterium Zymomonas mobilis for identifying pulque production/consumption in pottery vessels. Gas chromatography-mass spectrometry selected ion monitoring (m/z 191) of lipid extracts of >300 potsherds revealed characteristic bacteriohopanoid distributions in a subset of 14 potsherds. This hopanoid biomarker approach offers a new means of identifying commonly occurring bacterially fermented alcoholic beverages worldwide, including palm wine, beer, cider, perry, and other plant sap- or fruit-derived beverages [Swings J, De Ley J (1977) Bacteriol Rev 41(1):1-46].