Class Type Separation of the Polar and Apolar Components of Petroleum.

Identification of the heteroatom (nitrogen, sulfur, and oxygen)-containing compounds of petroleum is of key importance when considering industrial and environmental issues associated with crude oil production. The more commonly performed methods of crude oil fractionation are often insufficient in the extent to which they separate oils, not allowing defined "molecular" fractions to be obtained. Methods capable of performing a class type separation are uncommon and are often extensive and resource and time intensive. Here we report a method for the separation of crude oils into discrete compound classes. The method utilizes both ion exchange and normal phase chromatography to generate fractions of saturated hydrocarbons, aromatic hydrocarbons, basic compounds, naphthenic acids, and other oxygen-containing species, carbazoles, sulfones, and thiophenes from small crude oil samples (∼0.5 g). Assessment of method selectivity with a suite of model compounds has shown the fractions to be well-defined, with classes of model compounds isolated within discrete fractions. Application of the method to five crude oils of varying API gravity (12.1-38.3°) demonstrates a potential for wide-ranging use. Sample recoveries were high (77-98%) with simple evaporative losses correlating closely with total sample loss. Repeatability was also high, demonstrated by triplicate analyses of model compound mixtures, oils spiked with model compounds and oils alone. Separation selectivity was further demonstrated by application of the scheme to the Alaska North Slope (ANS) crude oil and analysis of fractions by comprehensive two-dimensional gas-chromatography mass-spectrometry (GC × GC/MS) and/or liquid-chromatography high-resolution accurate-mass mass-spectrometry methods (LC-HRAM-MS). Isolation of discrete fractions then allowed excellent separation (by LC and GC methods) of carbazole, dibenzothiophene, fluorenones, xanthones, and quinoline fractions. Individual parent and C1-5 alkyl homologues were easily separated (GC × GC/MS), allowing high-quality mass spectra (EI) to be obtained for the individual compounds in many cases. Analysis of fractions by GC × GC/MS also allowed a series of thioxanones to be identified.

Volatile and semi-volatile components of jetsam ambergris.

Volatile and semi-volatile compounds account for the odors, long valued in the perfumery industry, of the natural product, ambergris. Here we demonstrate application of solid phase micro extraction (SPME) and gas chromatography-mass spectrometry (GC-MS) to headspace analysis of the volatiles and semi-volatiles of jetsam ambergris. The samples collected in 2017/2018, ranged from a black, sticky material from New Zealand, likely recently ejected from a sperm whale, to a white solid found on a beach in Chile and radiocarbon-dated previously to be about 1000 years old. The traces of volatile/semi-volatile compounds extracted included, odorous γ-dihydroionone and odor-free pristane (2,6,10,14-tetramethylpentadecane), as the major constituents. The ratios of these to one another and to many other minor constituents, varied, depending on sample color and age.

Leaching of flame-retardants from polystyrene debris: Bioaccumulation and potential effects on coral.

Marine plastic debris can act as a reservoir of chemical additives that can pose a potential threat to sensitive ecosystems such as coral reefs. A survey of foam macrodebris collected on beaches indeed revealed high concentrations of hexabromocyclododecanes (ΣHBCDD) in polystyrene (PS) samples (up to 1940 µg g-1). Results also showed that PS fragments can still leach over 150 ng g-1 d-1 of ΣHBCDD (primarily as the α-isomer) for relatively long durations, and that these additives are readily bioaccumulated and well-retained by corals. Despite significant HBCDD bioaccumulation in coral tissue, short-term exposure to HBCDD or PS leachate had no considerable effect on coral photosynthetic activity, symbiont concentration and chlorophyll content. Exposure to the PS leachate did however cause consistent polyp retraction in nubbins over the 5-day exposure. This response was not observed in animals exposed to HBCDD alone, suggesting that another constituent of the leachate stressed corals.

Accumulation and toxicity of monoaromatic petroleum hydrocarbons in early life stages of cod and haddock.

A multitude of recent studies have documented the detrimental effects of crude oil exposure on early life stages of fish, including larvae and embryos. While polycyclic aromatic hydrocarbons (PAHs), particularly alkyl PAHs, are often considered the main cause of observed toxic effects, other crude oil derived organic compounds are usually overlooked. In the current study, comprehensive two-dimensional gas chromatography coupled to mass spectrometry was applied to investigate the body burden of a wide range of petrogenic compounds in Atlantic haddock (Melanogrammus aeglefinus) and cod (Gadus morhua) embryos that had been exposed to sublethal doses of dispersed crude oil. Several groups of alkylated monoaromatic compounds (e.g. alkyl tetralins, indanes and alkyl benzenes), as well as highly alkylated PAHs, were found to accumulate in the fish embryos upon crude oil exposure. To investigate the toxicity of the monoaromatic compounds, two models (1-isopropyl-4-methyltetralin and 1-isopropyl-4-methylindane) were synthesized and shown to bioaccumulate and cause delayed hatching in developing embryos. Minor developmental effects, including craniofacial and jaw deformations and pericardial edemas, were also observed at the highest studied concentrations of the alkylindane.

Establishing a link between composition and toxicity of offshore produced waters using comprehensive analysis techniques - A way forward for discharge monitoring?

Extracts of produced waters from five mature Norwegian Sea oil fields were examined as total organic extracts (TOEs) and after fractionation into operationally-defined 'polar' and 'apolar' fractions. The TOEs and fractions were examined by gas chromatography (GC), GC-mass spectrometry (GC-MS), two dimensional GC-MS (GC × GC-MS) and liquid chromatography with high-resolution spectrometry (LC-HRMS) techniques. Low molecular weight aromatics, phenols and other common petroleum-derived hydrocarbons were characterized and quantified in the TOEs and fractions. In addition, a range of more uncommon polar and apolar constituents, including those likely derived from production chemicals, such as trithiolane, imidazolines and quaternary amine compounds (so-called 'quats'), were tentatively identified, using GC × GC-MS and LC-HRMS. The acute toxicity of the TOEs and subfractions was investigated using early life stages of the marine copepod Acartia tonsa. Toxicity varied significantly for different PW TOEs and subfractions. For some PWs, the toxicity was attributed mainly to the 'polar' components, while that of other PWs was associated mainly with the 'apolar' components. Importantly, the observed toxicity could not be explained by the presence of the commonly reported compounds only. Although, due to the vast chemical complexity even of the sub-fractions of the PW extracts, specific compounds driving the observed toxicity could be not be elucidated in this study, the proposed approach may suggest a way forward for future revisions of monitoring regimes for PW discharges.

Percutaneous treatment of long superficial femoral artery occlusive disease: efficacy of the Hemobahn stent-graft.

PURPOSE: To assess the efficacy of the Hemobahn stent-graft in the percutaneous treatment of long occlusive lesions of the superficial femoral artery (SFA). METHODS: Fifty-nine limbs in 54 patients (42 men; mean age 73.3+/-8.2 years, range 55.2-91.3) with 59 symptomatic SFA occlusions >10 cm in length were selected for percutaneous treatment with the Hemobahn stent-graft. The treated SFA was assessed for patency and degree of stenosis by color-flow duplex ultrasound prior to discharge and at 1, 3, and 6 months and yearly thereafter. The actuarial life-table method was used to derive primary and secondary patency rates. RESULTS: Primary technical success was achieved in 56 (95%) of 59 limbs on an intention-to-treat basis (2 access and 1 device failures). In the first 30 days, 4 (6.8%) stent-graft thromboses and 5 (8.5%) minor technical difficulties occurred. Up to 1 year, there were 15 (25.4%) primary occlusions, 7 (11.9%) of which were associated with restenosis. Cumulative primary patencies were 88%, 67%, and 58% at 1, 6, and 12 months, respectively; secondary patencies were 92%, 82%, and 73% at the same intervals. There was no statistically significant difference (p<0.05) in patency (primary or secondary) with respect to presenting symptoms, lesion length, stent-graft length, or distal runoff. CONCLUSIONS: Symptomatic long occlusive lesions of the SFA treated percutaneously with the Hemobahn stent-graft achieved good outcomes initially with a low complication rate. Primary and secondary patencies were similar to those reported for open synthetic femoropopliteal bypass procedures.