TY - JOUR T1 - Tracking the weathering of an oil spill with comprehensive two-dimensional gas chromatography JF - Environmental Forensics Y1 - 2006 A1 - Nelson, R. K. A1 - Kile, B. M. A1 - Plata, D. L. A1 - Sylva, S. P. A1 - Xu, L. A1 - Reddy, C. M. A1 - Gaines, R. B. A1 - Frysinger, G. S. A1 - Reichenbach, S. E. AB - Comprehensive two-dimensional gas chromatography (GC x GC) was used to investigate the Bouchard 120 oil spill. The latter occurred on April 25, 2003, when the barge Bouchard 120 spilled similar to 375,000 liters of No. 6 fuel oil into Buzzards Bay, Massachusetts. In order to gain a better understanding of the natural processes affecting the fate of the spilled product, we collected and analyzed oil-covered rocks from Nyes Neck beach in North Falmouth, Massachusetts. Here we discuss the data from samples collected on May 9, 2003, and six months later, on November 23, 2003. Along with standard two-dimensional gas chromatographic analysis, we employed unique data-visualization techniques such as difference, ratio, and addition chromatograms to highlight how evaporation, water washing, and biodegradation weathered the spilled oil. These approaches provide a new perspective to studying oil spills and aid attempts to remediate them. VL - 7 IS - 1 N1 - 032ldTimes Cited:62Cited References Count:21 JO - Tracking the weathering of an oil spill with comprehensive two-dimensional gas chromatography ER - TY - JOUR T1 - Moving-wire device for carbon isotopic analyses of nanogram quantities of nonvolatile organic carbon JF - Anal Chem Y1 - 2005 A1 - Sessions, A. L. A1 - Sylva, S. P. A1 - Hayes, J. M. AB - We describe a moving-wire analyzer for measuring 13C in dissolved, involatile organic materials. Liquid samples are first deposited and dried on a continuously spooling nickel wire. The residual sample is then combusted as the wire moves through a furnace, and the evolved CO2 is analyzed by continuous-flow isotope ratio mass spectrometry. A typical analysis requires 1 microL of sample solution and produces a CO2 peak approximately 5 s wide. The system can measure "bulk" delta13C values of approximately 10 nmol of organic carbon with precision better than 0.2 per thousand. For samples containing approximately 1 nmol of C, precision is approximately 1 per thousand. Precision and sensitivity are limited mainly by background noise derived from carbon within the wire. Instrument conditions minimizing that background are discussed in detail. Accuracy is better than 0.5 per thousand for nearly all dissolved analytes tested, including lipids, proteins, nucleic acids, sugars, halocarbons, and hydrocarbons. The sensitivity demonstrated here for 13C measurements represents a approximately 1000-fold improvement relative to existing elemental analyzers and should allow the use of many new preparative techniques for collecting and purifying nonvolatile biochemicals for isotopic analysis. VL - 77 IS - 20 N1 - Sessions, Alex LSylva, Sean PHayes, John MengResearch Support, U.S. Gov't, Non-P.H.S.2005/10/15 09:00Anal Chem. 2005 Oct 15;77(20):6519-27. JO - Moving-wire device for carbon isotopic analyses of nanogram quantities of nonvolatile organic carbon ER - TY - JOUR T1 - Comparative analysis of methane-oxidizing archaea and sulfate-reducing bacteria in anoxic marine sediments JF - Appl Environ Microbiol Y1 - 2001 A1 - Orphan, V. J. A1 - Hinrichs, K. U. A1 - Ussler, W. A1 - Paull, C. K. A1 - Taylor, L. T. A1 - Sylva, S. P. A1 - Hayes, J. M. A1 - DeLong, E. F. AB - The oxidation of methane in anoxic marine sediments is thought to be mediated by a consortium of methane-consuming archaea and sulfate-reducing bacteria. In this study, we compared results of rRNA gene (rDNA) surveys and lipid analyses of archaea and bacteria associated with methane seep sediments from several different sites on the Californian continental margin. Two distinct archaeal lineages (ANME-1 and ANME-2), peripherally related to the order Methanosarcinales, were consistently associated with methane seep marine sediments. The same sediments contained abundant (13)C-depleted archaeal lipids, indicating that one or both of these archaeal groups are members of anaerobic methane-oxidizing consortia. (13)C-depleted lipids and the signature 16S rDNAs for these archaeal groups were absent in nearby control sediments. Concurrent surveys of bacterial rDNAs revealed a predominance of delta-proteobacteria, in particular, close relatives of Desulfosarcina variabilis. Biomarker analyses of the same sediments showed bacterial fatty acids with strong (13)C depletion that are likely products of these sulfate-reducing bacteria. Consistent with these observations, whole-cell fluorescent in situ hybridization revealed aggregations of ANME-2 archaea and sulfate-reducing Desulfosarcina and Desulfococcus species. Additionally, the presence of abundant (13)C-depleted ether lipids, presumed to be of bacterial origin but unrelated to ether lipids of members of the order Desulfosarcinales, suggests the participation of additional bacterial groups in the methane-oxidizing process. Although the Desulfosarcinales and ANME-2 consortia appear to participate in the anaerobic oxidation of methane in marine sediments, our data suggest that other bacteria and archaea are also involved in methane oxidation in these environments. VL - 67 IS - 4 N1 - Orphan, V JHinrichs, K UUssler, W 3rdPaull, C KTaylor, L TSylva, S PHayes, J MDelong, E FengComparative StudyResearch Support, Non-U.S. Gov'tResearch Support, U.S. Gov't, Non-P.H.S.2001/04/03 10:00Appl Environ Microbiol. 2001 Apr;67(4):1922-34. U2 - PMC92814 JO - Comparative analysis of methane-oxidizing archaea and sulfate-reducing bacteria in anoxic marine sediments ER - TY - JOUR T1 - Molecular and isotopic analysis of anaerobic methane-oxidizing communities in marine sediments JF - Organic Geochemistry Y1 - 2000 A1 - Hinrichs, K. U. A1 - Summons, R. E. A1 - Orphan, V. A1 - Sylva, S. P. A1 - Hayes, J. M. AB - Convergent lines of molecular, carbon-isotopic, and phylogenetic evidence have previously indicated (Hinrichs, K.U., Hayes, J.M., Sylva, S.P., Brewer. P.G.. DeLong, E.F., 1999. Methane-consuming archaebacteria in marine sediments. Nature 398, 802-805.) that archaea are involved in the anaerobic oxidation of methane in sediments from the Eel River Basin. offshore northern California. Now, further studies of those same sediments and of sediments from a methane seep in the Santa Barbara Basin have confirmed and extended those results. Mass spectrometric and chromatographic analyses of an authentic standard of sn-2-hydroxyarchaeol (hydroxylated at C-3 in the sn-2 phytanyl moiety) have confirmed our previous, tentative identification of this compound but shown that the previously examined product was the mono-TMS, rather than di-TMS, derivative. Further analyses of C-13-depleted lipids, appreciably more abundant in samples from the Santa Barbara Basin, have shown that the archaeal lipids are accompanied by two sets of products that are only slightly less depleted in C-13. These are additional glycerol ethers and fatty acids. The alkyl substituents in the ethers (mostly monoethers, with some diethers) are non-isoprenoidal. The carbon-number distributions and isotopic compositions of the alkyl substituents and of the fatty acids are similar, suggesting strongly that they are produced by the same organisms. Their structures, n-alkyl and methyl-branched n-alkyl, require a bacterial rather than archaeal source. The non-isoprenoidal glycerol ethers are novel constituents in marine sediments but have been previously reported in thermophilic, sulfate- and nitrate-reducing organisms which lie near the base of the rRNA-based phylogenetic tree. Based on previous observations that the anaerobic oxidation of methane involves a net transfer of electrons from methane to sulfate, it appears likely that the non-archaeal, C-13-depleted lipids are products of one or more previously unknown sulfate-reducing bacteria which grow syntrophically with the methane-utilizing archaea. Their products account for 50% of the fatty acids in the sample from the Santa Barbara Basin. At all methane-seep sites examined, the preservation of aquatic products is apparently enhanced because the methane-oxidizing consortium utilizes much of the sulfate that would otherwise be available for remineralization of materials from the water column. Crown Copyright (C) 2000 Published by Elsevier Science Ltd. All rights reserved. VL - 31 IS - 12 N1 - 384quTimes Cited:204Cited References Count:49 JO - Molecular and isotopic analysis of anaerobic methane-oxidizing communities in marine sediments ER - TY - JOUR T1 - Methane-consuming archaebacteria in marine sediments JF - Nature Y1 - 1999 A1 - Hinrichs, K. U. A1 - Hayes, J. M. A1 - Sylva, S. P. A1 - Brewer, P. G. A1 - DeLong, E. F. AB - Large amounts of methane are produced in marine sediments but are then consumed before contacting aerobic waters or the atmosphere. Although no organism that can consume methane anaerobically has ever been isolated, biogeochemical evidence indicates that the overall process involves a transfer of electrons from methane to sulphate and is probably mediated by several organisms, including a methanogen (operating in reverse) and a sulphate-reducer (using an unknown intermediate substrate). Here we describe studies of sediments related to a decomposing methane hydrate. These provide strong evidence that methane is being consumed by archaebacteria that are phylogenetically distinct from known methanogens. Specifically, lipid biomarkers that are commonly characteristic of archaea are so strongly depleted in carbon-13 that methane must be the carbon source, rather than the metabolic product, for the organisms that have produced them. Parallel gene surveys of small-subunit ribosomal RNA (16S rRNA) indicate the predominance of a new archael group which is peripherally related to the methanogenic orders Methanomicrobiales and Methanosarcinales. VL - 398 IS - 6730 N1 - Hinrichs, K UHayes, J MSylva, S PBrewer, P GDeLong, E FengResearch Support, Non-U.S. Gov'tResearch Support, U.S. Gov't, Non-P.H.S.England1999/05/11 02:03Nature. 1999 Apr 29;398(6730):802-5. JO - Methane-consuming archaebacteria in marine sediments ER -