Hayes
John M.
Hayes
John M.
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ArticleAn Introduction to Isotopic Calculations(Woods Hole Oceanographic Institution, 2004-09-30) Hayes, John M.These notes provide an introduction to: • Methods for the expression of isotopic abundances, • Isotopic mass balances, and • Isotope effects and their consequences in open and closed systems.
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ArticleCompound-specific radiocarbon dating of the varved Holocene sedimentary record of Saanich Inlet, Canada(American Geophysical Union, 2004-05-01) Smittenberg, R. H. ; Hopmans, Ellen C. ; Schouten, Stefan ; Hayes, John M. ; Eglinton, Timothy I. ; Sinninghe Damste, Jaap S.The radiocarbon contents of various biomarkers extracted from the varve-counted sediments of Saanich Inlet, Canada, were determined to assess their applicability for dating purposes. Calibrated ages obtained from the marine planktonic archaeal biomarker crenarchaeol compared favorably with varve-count ages. The same conclusion could be drawn for a more general archaeal biomarker (GDGT-0), although this biomarker proved to be less reliable due to its less-specific origin. The results also lend support to earlier indications that marine crenarchaeota use dissolved inorganic carbon (DIC) as their carbon source. The average reservoir age offset ΔR of 430 years, determined using the crenarchaeol radiocarbon ages, varied by ±110 years. This may be caused by natural variations in ocean-atmosphere mixing or upwelling at the NE Pacific coast but variability may also be due to an inconsistency in the marine calibration curve when used at sites with high reservoir ages.
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ArticleRapid analysis of 13C in plant-wax n-alkanes for reconstruction of terrestrial vegetation signals from aquatic sediments(American Geophysical Union, 2004-10-15) McDuffee, Kelsey E. ; Eglinton, Timothy I. ; Sessions, Alex L. ; Sylva, Sean P. ; Wagner, Thomas ; Hayes, John M.Long-chain, odd-carbon-numbered C25 to C35 n-alkanes are characteristic components of epicuticular waxes produced by terrestrial higher plants. They are delivered to aquatic systems via eolian and fluvial transport and are preserved in underlying sediments. The isotopic compositions of these products can serve as records of past vegetation. We have developed a rapid method for stable carbon isotopic analyses of total plant-wax n-alkanes using a novel, moving-wire system coupled to an isotope-ratio mass spectrometer (MW-irMS). The n-alkane fractions are prepared from sediment samples by (1) saponification and extraction with organic solvents, (2) chromatographic separation using silica gel, (3) isolation of straight-chain carbon skeletons using a zeolite molecular sieve, and (4) oxidation and removal of unsaturated hydrocarbons with RuO4. Short-chain n-alkanes of nonvascular plant origin (
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ArticleComparative analysis of methane-oxidizing archaea and sulfate-reducing bacteria in anoxic marine sediments(American Society for Microbiology, 2001-04) Orphan, Victoria J. ; Hinrichs, Kai-Uwe ; Ussler, William ; Paull, Charles K. ; Taylor, L. T. ; Sylva, Sean P. ; Hayes, John M. ; DeLong, Edward F.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 13C-depleted archaeal lipids, indicating that one or both of these archaeal groups are members of anaerobic methane-oxidizing consortia. 13C-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 13C 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 13C-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.
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ArticleAntarctic sediment chronology by programmed-temperature pyrolysis : methodology and data treatment(American Geophysical Union, 2008-04-02) Rosenheim, Brad E. ; Day, Mary Beth ; Domack, Eugene ; Schrum, Heather ; Benthien, Albert ; Hayes, John M.We report a detailed programmed-temperature pyrolysis/combustion methodology for radiocarbon (14C) dating of Antarctic sub-ice shelf sediments. The method targets the autochthonous organic component in sediments that contain a distribution of acid-insoluble organic components from several sources of different ages. The approach has improved sediment chronology in organic-rich sediments proximal to Antarctic ice shelves by yielding maximum age constraints significantly younger than bulk radiocarbon dates from the same sediment horizons. The method proves adequate in determining isotope ratios of the pre-aged carbon end-member; however, the isotopic compositions of the low-temperature measurements indicate that no samples completely avoided mixing with some proportion of pre-aged organic material. Dating the unresolved but desired young end-member must rely on indirect methods, but a simple mixing model cannot be developed without knowledge of the sedimentation rate or comparable constraints. A mathematical approach allowing for multiple mixing components yields a maximum likelihood age, a first-order approximation of the relative proportion of the autochthonous component, and the temperature at which allochthonous carbon begins to volatilize and mix with the autochthonous component. It is likely that our estimation of the cutoff temperature will be improved with knowledge of the pyrolysis kinetics of the major components. Chronology is improved relative to bulk acid-insoluble organic material ages from nine temperature interval dates down to two, but incorporation of inherently more pre-aged carbon in the first division becomes more apparent with fewer and larger temperature intervals.
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PreprintEvidence for substantial intramolecular heterogeneity in the stable carbon isotopic composition of phytol in photoautotrophic organisms( 2007-09-05) Schouten, Stefan ; Ozdirekcan, Suat ; van der Meer, Marcel T. J. ; Blokker, Peter ; Baas, Marianne ; Hayes, John M. ; Sinninghe Damste, Jaap S.The ubiquitous isoprenoid phytol was isolated from a range of algae, terrestrial plants and a bacterium and its two terminal carbon atoms were quantitatively removed by chemical oxidation. The product, 6,10,14-trimethylpentadecan-2-one, was depleted in 13C by 1-4‰ relative to the parent phytol. This difference is significant, and indicates that the pathway for biosynthesis of phytol induces substantial intramolecular stable carbon isotopic fractionations. The nature and magnitude of the fractionations suggest strongly that it is associated both with the biosynthesis of isopentenyl pyrophosphate via the 2-C-methylerythritol-4-phosphate pathway and with the formation of carotenoids and phytol from geranyl-geraniolphosphate. As a result of these large, intramolecular isotopic differences, diagenetic products formed by loss of C, such as pristane, may be naturally depleted in 13C by several permil relative to phytane.
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PreprintMechanism for nitrogen isotope fractionation during ammonium assimilation by Escherichia coli K12( 2013-03-25) Vo, Jason ; Inwood, William ; Hayes, John M. ; Kustu, SydneyOrganisms that use ammonium as the sole nitrogen source discriminate between [15N] and [14N] ammonium. This selectivity leaves an isotopic signature in their biomass that depends on the external concentration of ammonium. To dissect how differences in discrimination arise molecularly, we examined a wild-type (WT) strain of Escherichia coli K12 and mutant strains with lesions affecting ammonium-assimilatory proteins. We used isotope ratio mass spectrometry (MS) to assess the nitrogen isotopic composition of cell material when the strains were grown in batch culture at either high or low external concentrations of NH3 (achieved by controlling total NH4Cl and pH of the medium). At high NH3 (≥0.89 µM), discrimination against the heavy isotope by the WT strain (−19.2‰) can be accounted for by the equilibrium isotope effect for dissociation of NH4+ to NH3 + H+. NH3 equilibrates across the cytoplasmic membrane, and glutamine synthetase does not manifest an isotope effect in vivo. At low NH3 (≤0.18 µM), discrimination reflects an isotope effect for the NH4+ channel AmtB (−14.1‰). By making E. coli dependent on the low-affinity ammonium-assimilatory pathway, we determined that biosynthetic glutamate dehydrogenase has an inverse isotope effect in vivo (+8.8‰). Likewise, by making unmediated diffusion of NH3 across the cytoplasmic membrane rate-limiting for cell growth in a mutant strain lacking AmtB, we could deduce an in vivo isotope effect for transport of NH3 across the membrane (−10.9‰). The paper presents the raw data from which our conclusions were drawn and discusses the assumptions underlying them.
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ArticleSignature lipids and stable carbon isotope analyses of Octopus Spring hyperthermophilic communities compared with those of aquificales representatives(American Society for Microbiology, 2001-11) Jahnke, Linda L. ; Eder, Wolfgang ; Huber, Robert ; Hope, Janet M. ; Hinrichs, Kai-Uwe ; Hayes, John M. ; Des Marais, David J. ; Cady, Sherry L. ; Summons, Roger E.The molecular and isotopic compositions of lipid biomarkers of cultured Aquificales genera have been used to study the community and trophic structure of the hyperthermophilic pink streamers and vent biofilm from Octopus Spring. Thermocrinis ruber, Thermocrinis sp. strain HI 11/12, Hydrogenobacter thermophilus TK-6, Aquifex pyrophilus, and Aquifex aeolicus all contained glycerol-ether phospholipids as well as acyl glycerides. The n-C20:1 and cy-C21 fatty acids dominated all of the Aquificales, while the alkyl glycerol ethers were mainly C18:0. These Aquificales biomarkers were major constituents of the lipid extracts of two Octopus Spring samples, a biofilm associated with the siliceous vent walls, and the well-known pink streamer community (PSC). Both the biofilm and the PSC contained mono- and dialkyl glycerol ethers in which C18 and C20 alkyl groups were prevalent. Phospholipid fatty acids included both the Aquificales n-C20:1 and cy-C21, plus a series of iso-branched fatty acids (i-C15:0 to i-C21:0), indicating an additional bacterial component. Biomass and lipids from the PSC were depleted in 13C relative to source water CO2 by 10.9 and 17.2per thousand , respectively. The C20-21 fatty acids of the PSC were less depleted than the iso-branched fatty acids, 18.4 and 22.6per thousand , respectively. The biomass of T. ruber grown on CO2 was depleted in 13C by only 3.3per thousand relative to C source. In contrast, biomass was depleted by 19.7per thousand when formate was the C source. Independent of carbon source, T. ruber lipids were heavier than biomass (+1.3per thousand ). The depletion in the C20-21 fatty acids from the PSC indicates that Thermocrinis biomass must be similarly depleted and too light to be explained by growth on CO2. Accordingly, Thermocrinis in the PSC is likely to have utilized formate, presumably generated in the spring source region.
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PreprintProgress on a gas-accepting ion source for continuous-flow accelerator mass spectrometry( 2007-02) Roberts, Mark L. ; Schneider, Robert J. ; von Reden, Karl F. ; Wills, J. S. C. ; Han, Baoxi ; Hayes, John M. ; Rosenheim, Brad E. ; Jenkins, William J.A gas-accepting microwave-plasma ion source is being developed for continuous-flow Accelerator Mass Spectrometry (AMS). Characteristics of the ion source will be presented. Schemes for connecting a gas or liquid chromatograph to the ion source will also be discussed.
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PreprintThe pathway of carbon in nature( 2006-05-03) Hayes, John M.A “Perspective” for Science, introducing the paper "Biomarker Evidence for a Major Preservation Pathway of Sedimentary Organic Carbon," by Y. Hebting, P. Schaeffer, A. Behrens, P. Adam, G. Schmitt, P. Schneckenburger, S. Bernasconi, and P. Albrecht.
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PreprintThe carbon cycle and associated redox processes through time( 2006-01-24) Hayes, John M. ; Waldbauer, Jacob R.Earth’s biogeochemical cycle of carbon delivers both limestones and organic materials to the crust. In numerous, biologically catalyzed redox reactions, hydrogen, sulfur, iron, and oxygen serve prominently as electron donors and acceptors. The progress of these reactions can be reconstructed from records of variations in the abundance of 13C in sedimentary carbonate minerals and organic materials. Because the crust is always receiving new CO2 from the mantle and a portion of it is being reduced by photoautotrophs, the carbon cycle has continuously released oxidizing power. Most of it is represented by Fe3+ that has accumulated in the crust or been returned to the mantle via subduction. Less than 3% of the estimated, integrated production of oxidizing power since 3.8 Ga is represented by O2 in the atmosphere and dissolved in seawater. The balance is represented by sulfate. The accumulation of oxidizing power can be estimated from budgets summarizing inputs of mantle carbon and rates of organic-carbon burial, but levels of O2 are only weakly and indirectly coupled to those phenomena and thus to carbon-isotopic records. Elevated abundances of 13C in carbonate minerals ~2.3 Gyr old, in particular, are here interpreted as indicating the importance of methanogenic bacteria in sediments rather than increased burial of organic carbon.
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ArticleAn evaluation of 14C age relationships between co-occurring foraminifera, alkenones, and total organic carbon in continental margin sediments(American Geophysical Union, 2005-01-25) Mollenhauer, Gesine ; Kienast, Markus ; Lamy, Frank ; Meggers, Helge ; Schneider, Ralph R. ; Hayes, John M. ; Eglinton, Timothy I.Radiocarbon age relationships between co-occurring planktic foraminifera, alkenones and total organic carbon in sediments from the continental margins of Southern Chile, Northwest Africa and the South China Sea were compared with published results from the Namibian margin. Age relationships between the sediment components are site-specific and relatively constant over time. Similar to the Namibian slope, where alkenones have been reported to be 1000 to 4500 years older than co-occurring foraminifera, alkenones were significantly (~1000 yrs) older than co-occurring foraminifera in the Chilean margin sediments. In contrast, alkenones and foraminifera were of similar age (within 2σ error or better) in the NW African and South China Sea sediments. Total-organic-matter and alkenone ages were similar off Namibia (age difference TOC-alkenones: 200-700 years), Chile (100-450 years), and NW Africa (360-770 years), suggesting minor contributions of pre-aged terrigenous material. In the South China Sea total organic carbon is significantly (2000-3000 yrs) older due to greater inputs of pre-aged terrigenous material. Age offsets between alkenones and planktic foraminifera are attributed to lateral advection of organic matter. Physical characteristics of the depositional setting, such as sea-floor morphology, shelf width, and sediment composition, may control the age of co-occurring 2 sediment components. In particular, offsets between alkenones and foraminifera appear to be greatest in deposition centers in morphologic depressions. Aging of organic matter is promoted by transport. Age offsets are correlated with organic richness, suggesting that formation of organic aggregate is a key process.
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ArticleOrganic carbon aging during across‐shelf transport(John Wiley & Sons, 2018-08-22) Bao, Rui ; Uchida, Masao ; Zhao, Meixun ; Haghipour, Negar ; Montlucon, Daniel B. ; McNichol, Ann P. ; Wacker, Lukas ; Hayes, John M. ; Eglinton, Timothy I.Compound‐specific radiocarbon analysis was performed on different grain‐size fractions of surficial sediments to examine and compare lateral transport times (LTTs) of organic carbon. 14C aging of long‐chain leaf wax fatty acids along two dispersal pathways of fluvially derived material on adjacent continental margins implies LTTs over distances of ~30 to 500 km that range from hundreds to thousands of years. The magnitude of aging differs among grain size fractions. Our finding suggests that LTTs vary both temporally and spatially as a function of the specific properties of different continental shelf settings. Observations suggest that 14C aging is widespread during lateral transport over continental shelves, with hydrodynamic particle sorting inducing age variations among organic components residing in different grain sizes. Consideration of these phenomena is of importance for understanding carbon cycle processes and interpretation on sedimentary records on continental margins.