DCO Project Summary

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Project Title
Global Distribution of Abiotic Carbon Compounds, H2 and Noble Gases
Start DateEnd Date
2013-07-01 2015-06-30
NameRoleInstitutionDCO ID
Related GrantsDCO ID
11121/9902-5454-7041-1832-CC
Description

This research will address (1) the role of water-rock reactions, with a specific focus on serpentinization, in the production of reduced gases including hydrogen and methane, (2) the rates of reaction in low- and high-temperature systems, mafic and ultramafic terrains, and in rocks of varying degrees of age and alteration, and (3) the development of models of reduced gas flux on a global scale.

Key global sample sites (continental; oceanic) will be identified that provide gases, fluids, and solids that can be interrogated with multiple methods to assess the three areas identified above. The team will use gas and fluid isotope (stable and noble) geochemistry including isotopologues, mineralogy and mineral chemistry, bulk rock chemistry, and micro-imagining and spectroscopy.

Project UpdatesClick to add Project Update

Reporting Year 2014 Click to expand


  • RY2014-1 - submitted on Apr 01, 2014

    Update Details:

    [2014-04-01] The IPGP team conducted on site sample and geochemistry tests of fluids and gases at Dziani Dzaha Lake, Mayotte Island (Madagascar).
  • RY2014-3 - submitted on Aug 08, 2014

    Update Details:

    [08 August 2014]

    University of Toronto (Prof. Barb Sherwood Lollar, Lead). This year our team has continued fieldwork at the Kidd Creek mine in Timmins, as well as targeting two new sites in the Sudbury Basin. The team has worked on characterizing the geochemical profiles of the water and gas samples collected, in particular with regards to elemental characterization and δ13C and δ2H analysis carried out at the University of Toronto. These new samples from Sudbury, along with those from deeper levels of the Kidd Creek Mine, have proven to be extremely interesting - the results of which were presented in talks given by the new DCO-funded postdoc C. Sutcliffe (started December 2013) at the Canadian Astrobiology Training Program in Montreal and at the Goldschmidt 2014 conference in Sacramento, and have since garnered international press attention, e.g., Issue 2976 of the New Scientist (http://www.newscientist.com/article/mg22329762.600-ancient-water-cache-may-be-pristine-primordial-soup.html#.U8gSCC-61Cc) and currently being written up by the Guardian in the United Kingdom.  In addition to the attention garnered by Sutcliffe’s work there was considerable impact both academically and in the popular sphere from the clumped methane isotopologue work through sponsorship by the DCO of three teams – Ono (MIT), Eiler (CalTech), and Young-Rimble (UCLA). The isotopologue session at Goldschmidt was a highlight of the meeting.

           Current and future collaborations and analyses: Within these fieldtrips, in addition to ongoing collaborations with C.J. Ballentine’s group at Oxford, UK for noble gas analyses, new collaborations were set up with microbiologists from Penn State University (Regina Wilpiszeski and Dr. Chris House, Lead PI on the Penn State NASA Astrobiology team) and the University of Ghent (Gaetan Borgonie). Additional current collaborations include the development of the isotopologue technique with Shuhei Ono and his team at M.I.T. and the measurement of stable S isotopes with Long Li at the University of Alberta. Plans for future analyses and collaborations include the measurement of radiogenic and stable Sr isotopes by C. Sutcliffe with Kevin Burton at the University of Durham (September 2014), analysis of S isotopes by C. Sutcliffe with Shuhei Ono at M.I.T (fall this year), and analysis of N isotopes by C. Sutcliffe at Toronto. A new DCO funded postdoc, starting October 2014, will be working on VFA analysis of several sample sets in an ongoing collaboration between Deep Energy researchers (Sherwood Lollar, Ballentine) and Deep Life Co-Chair Kai Hinrichs and Verena Hauer at Bremen. Future fieldwork plans include continued sampling trips to all three mines, in addition to new targets such as Red Lake, Ontario. 

    University of Oxford (Prof. Chris Ballentine, Lead). In May 2013 we published  a DCO supported paper in Nature paper reporting the oldest free (carbon rich) fluids yet discovered (In collaboration with Barb Sherwood Lollar’s DCO team in Toronto) using new and groundbreaking multi-collector technology in noble gas isotope determination (Holland et al., 2013). Following this publication we saw a huge amount of press interest and fielded many enquiries through the summer of 2013. This effort was rewarded with the paper being highlighted as one of the top ten science stories of 2013 by media groups (e.g. http://news.discovery.com/tech/the-10-best-science-stories-of-2013-131231.htm). 

    From August 1, 2013, I formally moved from the University of Manchester to take up the Chair of Geochemistry at Oxford. This has been with some inevitable disruption to my research program but provides an opportunity to build a new laboratory with state of the art multi-collector noble gas isotope mass spectrometers that builds on, amongst others (see report by Igor Tolstikhin), in the successful application demonstrated by the Holland et al paper. The new laboratory directly underpins the DCO work and has leveraged a value of £840,000 of new equipment (Helic-SFT, Argus, Automatic sample preparation module) in new laboratory space that has a value of £400,000 with additional equipment purchased on an ERC grant at Manchester transferred to Oxford with a value of £750,000.

    In spring of 2014 we successfully concluded negotiations with Exxon-Mobile to fund a postdoctoral position for two years to investigate the use of noble gases in developing hydrocarbon exploration strategies. This has a value of £320,000 (with possibilities of extension) and is more clear leverage of the support that DCO has funded to date. The new Exxon postdoc has been in place for two weeks at the time of writing and will provide excellent future synergies with the DCO post.

    I have already reported to the DCO the success of lobbying the UK government research funding body, NERC, to invest £8million over five years in understanding volatile elements in the deep Earth and the role they play in Earth’s surface habitability – with carbon of course being a key volatile component. I can now report that through open competition, and with DCO support, I have successfully led an Oxford bid to the value of £2.25million to place constraints on volatile cycling into and out of the Earth’s mantle. This program will start in September and involves 20 Co-Is from 10 UK universities and international partners that include Eric Hauri, director of DCO Reservoirs and Fluxes.

    Kola Center (Dr. Igor Tolstikhin, Lead). During the first year we worked on three topics. 

    1. As reported last autumn, we realized that we must check the database throughout.  Accordingly, we reviewed all data related to approx. 6000 samples out of 6729 samples available in the database in the last summer (June 01, 2013); this has mainly been done by B. Piolyak and O.Kikvadze (4300 samples), but I and M. Vetrina also participated (1700).  There is no doubt that this work will be finished in late autumn and the database can be opened in Internet for users afterwards. 

    2. We continue compilation of new data (Polyak and Kikvadze) and during last year 551 samples have been added to the database, so the total number of samples included is 7280. 

    3. Unfortunately the Review with preliminary title “Noble gas isotopes in hydrocarbon gases, oils and related ground waters” has not been finished yet, in contrast to our agreement in Manchester in February 01, 2013.  However substantial progress with this topic has been achieved and the first draft is almost complete.  To approve some delay of this work, I would like to mention, that this Review is not just compilation of what has been done, but includes original issues. 

      Recently the manuscript has been processed by all co-authors, Chris Ballentine, Boris Polyak (twice), and Edvard Prasolov. I improved it in accord with their comments, produce the list of references and now we have the next draft. We have to finish the last relatively short Chapter and then prepare the manuscript for submission.

    Institut de Physique du Globe de Paris, IPGP (Dr. Benedicte Menez, Lead).

    Reactions and carbon transfers at the macro- and micro-environment scales in natural samples from the oceanic lithosphere:

    • Valorization by the group of B. Ménez of the results obtained on the hydrothermal field of Prony (New Caledonia) through three publications (Quéméneur et al. 2014; Monnin et al., 2014; Pisapia et al., 2014). These first three papers respectively describe the hydrothermal fluid chemistry, the microbial ecology, and the geobiology along with the mineralogy. This system corresponds to an exciting example of alkaline fluids produced by serpentinization reactions with meteoric water in ultramafic rocks that in turn react with coastal seawater to form spectacular brucite carbonate structures.

    Associated collaboration & networking: work performed by an interdisciplinary research team affiliated with the Institute of Research for Development (IRD, Nouméa, New Caledonia), the Mediterranean Institute of Oceanography (MIO, Marseille, France), the CNRS-GET lab from Toulouse University (France), the Institut de Physique du Globe de Paris (IPGP) and the Institut de Minéralogie et de Physique des Milieux Condensés (IMPMC, Paris, France).

    • Development by the group of B. Ménez of the FISH-guided laser capture microdissection of single-cell and subsequent genome sequencing in order to gain insights into the diversity and functioning of serpentinization-hosted microbial populations and fully understand their role in the deep carbon and nitrogen cycles (applied to the Prony samples).

    Associated collaboration & networking: work performed in collaboration with P. López-García and D. Moreira from the “Ecologie Systématique et Evolution” laboratory in Paris-Sud 11 University (France). D. Emerson (Bigelow Laboratory for Ocean Sciences, East Boothbay, Maine) will also be invited for one month at IPGP to share expertise.

    • Experiments on DISCO beamline (synchrotron SOLEIL, France) using single- or two-photon spectroscopy and deep UV microscopy on drilled oceanic serpentinites (Atlantis Massif, Mid-Atlantic Ridge, 30°N) in order to characterize the organic carbon (geobiology group, papers in progress)

    Associated collaboration & networking: a strong collaboration was formally established with F. Jamme and M. Réfrégiers (synchrotron SOLEIL, France) with notably a cofunded 2-year postdoc.

    • Study of the carbonation reactions of serpentinites sampled along active detachment systems located at the South Western Indian Ridge (SWIR, 64°35'E ) investigated during the SMOOTHSEAFLOOR cruise (PI: D. Sauter and M. Cannat). In this framework M. Cannat and I. Martinez supervised a Master's degree student from IPGP (Valérie Payré) to carefully study the carbonate-serpentine contacts in brecciated samples. Using the techniques developed by B. Ménez and her group, we also started the study of the C careers in drilled samples from basaltic crust (Hole 1256D) where carbon concentration and isotopic composition was measured (Shilobreeva et al., 2011). Several evidences for reduced carbon were observed; this work is still in progress and needs to be continued in the coming months.

    • During year 1 the marine geosciences group conducted a major oceanographic cruise (ODEMAR; PI: J. Escartin) to study oceanic detachments along the Mid-Atlantic Ridge in the 13°N area (Nov-Dec 2013). During the cruise we recovered rock samples, fluid samples from hydrothermal vents, and geophysical data. Data processing, sample analyses, and interpretations are ongoing.

    • D. Brunelli’s group (Modena) conducted major and trace element analyses of relic primary minerals of a large collection of mantle peridotites. Sample collection is from eastern SWIR (SMOOTHSEAFLOOR), central SWIR (Andrew Bain) and western SWIR (Bouvet Triple Junction). Modelling for the melting, and melt extraction processes was carried out (paper in progress).

    California Institute of Technology Caltech (Dr. Max Coleman, co-Lead). We have been analyzing the material recovered from the research cruise to the Mid-Cayman trough in summer 2013, supported by a separate DCO grant. Through the DCO support we renewed the collaboration with Dr. Cindy Van Dover who made another research cruise to the same area later that year. She augmented our sample collection with more biological specimens. The analytical work was performed by two postdocs (Dr. Kathrin Streit and Dr. Emma Versteegh), supported by a NASA award with some of the sample preparation costs supported by the DCO grant. The focus of the work was to detail part of the carbon geochemical cycle, specifically to understand the food web, how the hydrothermal vent fluids contributed to support the ecosystem and why carbon isotope compositions of the organisms did not reflect the trophic chain as described by sulfur and nitrogen isotopes.

    We separated individual lipid fatty acids and from different parts of the vent shrimp species, Rimicaris hybisae, and analyzed their carbon isotope compositions. The shrimp generally relied on the chemosynthetic bacteria for their organic carbon input. There were significant differences in carbon isotopic values of chemosynthetically derived fatty acids between vent fields, which implies that the vent chemistry has a major influence on the microbial community composition, including the dominant carbon fixation pathways used. Further, detailed work investigated the difference in diet of the majority of the shrimp, clustered in dense swarms, relative to those sparsely distributed not very far far away. We analyzed carbon, nitrogen and sulfur isotope compositions of various parts of the shrimp and their gut contents. The densely packed shrimp depend solely on the chemosynthetic bacteria hosted in their specially-adapted gill covers. The sparse shrimp, contrary to received wisdom, were found to have remnants of other organisms in their guts and now must be seen to be carnivorous. The trophic chains can be perfectly described by the details of the C, N, and S isotopic characteristics and also explain the previously misunderstood carbon isotope values.

    Instituto Nazionale di Geofisica e Vulcanologia, INGV (Dr. Giuseppe Etiope, Lead). In July-August 2013 the specifications of gas sampling and storage for isotopologue analyses were defined in agreement with Caltech and MIT laboratories. Gas sampling was then carried out from seeps and springs in continental serpentinization sites in Greece (September 2013), Portugal (October 2013), Turkey (November 2013) and Italy (June 2014). Samples were sent to the project partners of Caltech and MIT for stable C and H isotopic and CH4 isotopologue analyses.

    Follow-up of the analyses and interpretation of the results provided by Caltech and MIT. Assessment of gas generation temperatures indicated by geologic and geochemical thermometers and their comparison with the temperatures suggested by isotopologue data. Sampling and provision of gas from high-temperature magmatic systems, especially for isotopologue and stable carbon and hydrogen composition of methane.

    ETH, Zurich (Prof. Gretchen Früh-Green, Lead). The group of Gretchen Früh-Green at the ETH Zurich is focusing research on distinguishing abiotic and biotic sources and sinks of carbon and studying processes of fluid-rock interaction in modern and ancient rocks of the oceanic lithosphere. This includes comparative field studies of geochemical and microbial processes during serpentinization and the precipitation of carbonate (±brucite) in two high alkaline, ultramafic environments: the active marine Lost City hydrothermal system (MAR, 30°N), and high alkaline, Ca-OH springs associated with present-day serpentinization and carbonate deposits in the Voltri Massif (Liguria, N. Italy). To identify carbon sources for microorganisms in the Lost City carbonate structures, lipid biomarkers that are diagnostic of methanogens and sulfate reducers have been isolated and their 14C content will soon be determined. A further goal has been to combine radiocarbon with stable isotope studies to determine whether the source of carbon for high concentrations of organic acids (formate, acetate) in the Lost City fluids is mantle-derived or seawater bicarbonate. This has also involved considerable method development. In addition, investigations using Scanning Electron Microscopy (SEM) highlight the close association between microbial biofilms, calcium carbonate, and brucite. In some instances, brucite forms long ropes that may be attributed to microbially influenced precipitation. In other instances, aragonite appears to precipitate first and then is covered by brucite. Dense biofilms are intimately linked with the growing minerals. These studies have involved collaborations with Susan Lang (ETH), Marvin Lilley (Univ. Washington), Matt Schrenk (DCO-Deep Life, E. Carolina Univ.), William Brazelton (now at Univ. Utah), Stefano Bernasconi (ETH) and Tomaso Bontognali (ETH), many of which are new to DCO. Results have been presented at Goldschmidt 2013, Fall AGU 2013, and Goldschmidt 2014, and abstracts will be submitted for Fall AGU 2014.

    Experimental work at ETH has been carried out in collaboration with Marvin Lilley (academic guest at ETH from Aug-Dec, 2013; May-June, 2014). Construction and testing of a custom-designed cryrogenic inlet system to concentrate gaseous phases and measure compound-specific isotopes by continuous-flow mass spectrometry has been completed. Measurements can now be made on fluids with a minimum concentration of 150nl CH4. Future work will be made to modify the system to measure C-O-H fluids from experimental capsules.

          Future Work. Planned work at the ETH includes completing radiocarbon measurements of the Lost City of isolated lipid biomarkers from the Lost City hydrothermal deposits and from methane sampled in the alkaline springs of the Voltri Massif. A number of manuscripts are in progress and will be finished in the next year of funding. A new project has been submitted to the Swiss National Science Foundations (SNSF) (planned start date: 1 Nov 2014) to combine microstructural studies of fluid and reaction pathways with in-situ probing to constrain microfracturing networks and heterogeneities of fluid-peridotite interactions in different tectonic settings. These data will be used to quantify mineralogical and chemical changes that control H2 production and the speciation, release or consumption of carbon during progressive serpentinization. Raman microspectroscopy, standard stable isotope analyses of bulk samples and in-situ ion microprobe analyses (SIMS and NanoSIMS) will be used to investigate the nature, composition and distribution of reduced carbon phases in rocks from the upper oceanic mantle, and to distinguish abiotic from biotic carbon in serpentinites. This project will also involve new collaborations within the DCO with Bénédicte Ménez (IPGP).

    China University of Geosciences, Beijing (Prof. Changshan Wang, Lead).

     

    1. Progress of SK-2 continental scientific drilling program: The SK-2 continental scientific drilling program is jointly funded by the International Continental Drilling Program (ICDP) and China Geological Survey since 2009. The objective of this program is to fully recover the lower Cretaceous strata of Songliao Basin to form the most complete terrestrial records of Cretaceous climate change when combined with that of SK-1. The wellsite of SK-2 is near Anda city, Daqing oilfield. The drilling began at 00:00 on April 13, 2014, using adiameter of 444.5 mm drill bit, water-based drilling fluid for the first time. The drilling was completed at 03:30 on April 30, 2014, at the well depth of 440.96 m as the formation is the fifth member of Nenjiang Formation. The well was spud-in on April 30, 2014, using a 311.1mm 3A drill bit, water-based drilling fluid for the second time. From May 17 to May 25, coring footage was 61.11 m, with 58.11 m of core recovered. The core recovery is 95.09%. The total coring footage of the second member of Nenjiang Formation was 73.65 m, with 58.11 m of core recovered. The core recovery is 78.9%. From June 3 using the technology of hydraulic hammer drill, coring footage is 9.51 m, core length is 9.51 m, and core recovery is 100%. From June 3 to July 18, 2014, rapid drilling to 2826.48 m, borehole diameter is 215.9 mm. From July 18 to July 24, 2014, bore hole to 1216.11 m, borehole diameter from 215.9 mm to 444.5 mm.
    2. Opening ceremony of SK-2 drilling program: The opening ceremony of SK-2 drilling program will be held in the morning of August 8th, 2014 in SK-2 drilling site in Daqing. The participants include (1) officials from the Ministry of Land and Resources of China, Ministry of Science and Technology of China, Ministry of Education of China, Natural Science Foundation of China; (2) About 20 scientists from ICDP organization, Deep Carbon Observatory, IUGS and other domestic and overseas universities, and the PIs of the SK-2 drilling program. The ceremony will be presided over by Jinfa Li, the vice Director of China Geological Survey. The delegates from all sides including leading PI, Prof. Chengshan Wang from China University of Geosciences at Beijing, will speak at the opening ceremony. Ziran Zhong, the director of China Geological Survey, will announce the opening of SK-2 drilling program.
    3. International Continental Scientific Drilling Workshop: All the scientists participating in the opening ceremony will attend the workshop held in the afternoon of August 8, 2014. Prof. Shunwen Dong from the Chinese Academy of Geological Sciences will introduce achievements of SinoProbe. Pro. Yildirim Dilek will give a talk on the current activities and future plans of International Union of Geological Sciences (IUGS) on deep drilling. Dr. Thomas Wiersberg from the International Continental Drilling Program (ICDP) will introduce the audience to the achievements and future plans of the program. Prof. Craig Schiffries will share with the participants the achievements and future plans of the Deep Carbon Observatory. Prof. Yasufumi Iryu from ICDP Japan and Dr. Youn Soo Lee from ICDP Korea will give a talk on the progress of deep drilling in Japan and Korea, respectively. Prof. Chengshan Wang, the leading PI of the SK-2 drilling program will present a talk titled “Deep Underground Laboratory in China: Status update on the Application Process.” Finally, the participants will make plans for the Deep Underground Laboratory workshop of 2015 in China with joint sponsorship by the ICDP and the Deep Carbon Observatory.

     

  • RY2014-2 - submitted on Aug 08, 2014

    Update Details:

    Publications (as of August 8 2014):

    • Arthur, M. and Cole, D. R. (2014) Unconventional hydrocarbon resources: Prospects and problems. Elements 10, 257-264.
    • Cole, D. R. and Arthur, M. A. (2014, editors) Unconventional Hydrocarbon Resources, Elements 10 (4). ISSN 1811-5209
    • Etiope, G. and Sherwood Lollar, B. (2013) Abiotic methane on Earth. Reviews of Geophysics 51(2): 276-299.    doi:10/1002/rog.20011.
    • Etiope G. and Schoell M. (2014). Abiotic gas: atypical but not rare. Elements, 10, 289-294
    • Galvez, M., Martinez, I., Beyssac, O., Benzerara, K., Agrinier, P., Assayag, N., (2013) Metasomatism and graphite formation at a lithological interface in Malaspina (Alpine Corsica, France), Contrib. Mineral. Petrol. DOI 10.1007/s00410-013-0949-3,.
    • Holland, G., Sherwood Lollar, B., Li, L., Lacrampe-Couloume, G., Slater, G.F. and Ballentine, C.J. (2013) Deep fracture fluids isolated in the crust since the Precambrian.  Nature 497(7449): 367-360.
    • Lang S.Q., Früh-Green G.L., Bernasconi S.M, Wacker L. (2013) Isotopic (δ13C, Δ14C) analysis of organic acids in marine samples using wet chemical oxidation. Limnology & Oceanography Methods, 11:161–175
    • Méhay S., Früh-Green G.L., Bernasconi S.M., Brazelton, W., Schaeffer P., Adam P. and Lang S.Q. (2013) Record of archaeal activity at the serpentinite-hosed Lost City Hydrothermal Field, Geobiology, 11:570-592.
    • Monnin C, Chavagnac V., Boulart C., Ménez B., Gérard M., Gérard E., Quéméneur M., Erauso G., Postec A., et al. (2014) The low temperature hyperalkaline hydrothermal system of the Prony bay (New Caledonia). Biogeosciences Discuss. 11, 6221-6267.
    • Ono, S., Wang, D.T., Gruen, D.S., Sherwood Lollar, B., Zahniser, M., McManus, B.J. and Nelson, D.D. (2014) Measurement of a Doubly-Substituted Methane Isotopologue, 13CH3D, by Tunable Infrared Laser Direct Absorption Spectroscopy. Analytical Chemistry. doi: 10.1021/ac5010579
    • Pasini V, Brunelli D, Dumas P, Sandt C, Frederick J, Benzerara K, Bernard S, Ménez B (2013) Low temperature hydrothermal oil and associated biological precursors in serpentinites from Mid-Ocean Ridge. Lithos, 06.014
    • Quémeneur M., Bes M., Postec A., Mei N., Hamelin, Monnin C., Chavagnac V., Payri C., Pelletier B., Guentas-Dombrowsky L., Gérard M., Pisapia C., Gérard E., Ménez B., Ollivier B., Erauso G. (2014) Spatial distribution of microbial communities in the shallow submarine alkaline hydrothermal field of the Prony Bay, New Caledonia. Environ. Microbiol. Reports, DOI: 10.1111/1758-2229.12184.
    • Schwarzenbach E.M., Lang S.Q., Früh-Green G.L., Lilley M.D., Bernasconi S.M, Méhay S. (2013) Sources and cycling of carbon in continental, serpentinite-hosted alkaline springs in the Voltri Massif, Italy, Lithos, 177:226–244.

Reporting Year 2015 Click to expand


  • Final Report Second DE project - submitted on Sep 15, 2015

    Update Details:

    The research in this portion of the second Deep Energy project addressed (i.) the role of water-rock reactions, with a specific focus on serpentinization, in the production of reduced gases including hydrogen and methane; (ii.) The rates of reaction in low and high temperature systems; in mafic and ultramafic terrains; and in rocks of varying degrees of age and alteration (young marine versus Phanerozoic and Precambrian continental systems); (iii.) The development of models of reduced gas flux on a global scale. Field programs will nurture experimental programs and, by identifying unique sample suites ranging from abiotic to biotic end-members and mixtures, will feed into the developments in isotopologue research.  This effort also has natural strong ties to the Deep Life’s studies of Rock Hosted Microbial Communities project. Furthermore there will be a shared interest in characterizing diversity of deep microbial communities in Precambrian cratons using deep DNA sequencing technology in connection with the DCO Census of Deep Life.

    Precambrian cratons

    Deep Energy funded landmark Nature papers (Holland, Sherwood Lollar1 and Ballentine 2013; Sherwood Lollar, Onstott and Ballentine, 2014) redefined the deep continental crust carbon-fluid landscape; demonstrating the existence of deep carbon-fluid regimes preserved up to planetary (Ga) timescales and identifying the Precambrian continental crust as a source of hydrogen that doubles the global budget from serpentinization and radiolysis. The most recent work during 2013-2015 provided a first examination of global H2 production via water-rock reaction (serpentinization and radiolysis) from the > 70% of the continental lithosphere that is Precambrian in age. Key to the discovery is the map of global occurrences of H2 (see below) and CH4-rich deep saline groundwaters.

    This first work on the role of Precambrian continental lithosphere as an energy source for both abiogenic and biogenic methane production doubled estimated global H2 production from serpentinization and radiolysis compared to previous estimates, identified this extra production to be in the under-explored continental crust, and provided a new foundation model for the Earth’s Carbon Budget. Global models such as this are key inputs for the Decadal Goals of the DCO for the Next Five Years. A major objective of the previous Deep Energy projects were to develop new techniques for defining the temporal and physical framework of deep carbon bearing fluid systems and derive a foundational estimate of the hydrogen production feedstock that drives both the Abiogenic Carbon cycle (via hydrogen driven reactions such as Fischer-Tropsch synthesis), and the Biological Deep Carbon cycle (as hydrogen sustains microbial communities that produce methane and higher hydrocarbons and in turn may be sustained by methanotrophy). Activities included both field work at mine sites across the Canadian Shield (in concert with Industrial Partners in the Mining Industry) and substantial efforts from the Stable Isotope Laboratory at Toronto to support the clumped methane isotopologue work at MIT and UCLA through provisions of isotopically characterized standard materials, key field samples and cross-calibration and ground-truthing of analytical developments reflected in two papers with the Ono Lab at MIT. Samples sent to UCLA are currently under analysis.

    Continuing this work, within the reporting period the Lollar-Ballentine team have extended our investigations to investigate the age and character of free fracture fluids through their noble gas content from more and deeper locations within the Kidd creek system (This first involved Dr Jon Fellowes who was succeeded by Dr Oliver Warr when Ballentine moved to Oxford). These include investigation of samples from the same flow analyzed by Holland at 7850 ft depth, and new samples from 9500 ft in the system which have become available with new mining operations. Additionally, samples have been collected from two mines in Sudbury: Nickel Rim (5675 feet) and Fraser Mine (4700 feet), also over an 11 month period. Results from these samples show fluids in the deep sections of the Kidd Creek mine to have indicators of yet greater age. Results from the Sudbury complex show some similar characteristics, showing the ubiquity of ancient deep fluids systems in the crust, but with important differences that reflect different age (younger) and geological setting (no 129Xe anomaly) compared to the Kidd Creek system. These samples, based on the preliminary results from the reporting period, are the focus of the next stage of recently funded investigation.

    It should be noted that due to the age of the systems, these samples have all accumulated radiogenic noble gas excess beyond that of any other terrestrial fluid. However, the absolute abundances of the non-radiogenic noble gases are very low. Ensuring all isotopes of each noble gas over this dynamic range were able to be determined has been analytically demanding on an unprecedented scale. Further complications were caused by the mid-project relocation to Oxford. This has required moving the GVI Helix mass spectrometer (the instrument used by Holland to obtain his results) from Manchester, as well as configuring two brand new mass spectrometers, the Helix SFT and Argus, for accurate noble gas determination. Oliver Warr, the DCO funded postdoc has now installed, calibrated and implemented in the reporting period a system that will serve as the basis for all future analyses of deep crustal carbon systems.

    Dr Jon Fellows in this reporting period also chaired and organized the first DCO early career scientist conference in Costa Rica https://deepcarbon.net/feature/meeting-report-early-career-scientist-workshop#.VZpQ4E1FCUk

    Terrestrial systems-geochemical data mining

    Noble gases are unique tracers of terrestrial volatiles used to study sources of natural gases, waters and oils, as well as processes governed formation, evolution and behavior of natural water reservoirs and hydrocarbon (HC) deposits.  During more than 50 years, since the first fundamental contribution by R.E. Zartman, G.J. Wasserburg and J.H.Reynold (1961), abundances of noble gas isotopes were measured in thousands of terrestrial fluids and discussed in 100th scientific contributions, thus improving our knowledge about origin and evolution of volatile components of our planet. 

    Two major objectives were envisaged within the frame of the noble gas sub-project: (i) to compile an experimental data, first of all results of measurements of He isotope composition in terrestrial fluids; (ii) to review scientific contributions discussing noble gas isotopes as tracers of terrestrial HC materials and related ground waters. In the course of DCO project 4560 new samples have been compiled and added into the pre-existing noble gas data base (NG DB), which at present amounts to 7262 samples.  This is far the largest NG data source now available to the world scientific community.  The NG DB includes data from published papers, dissertations, technical reports, electronic sources and those reported via private communications.  In most cases the NG DG presents coordinates of the samples, which allows visualization of the data (i.e., their presentation as maps)) and thus their comparison with other geochemical and / or geophysical characteristics of given region or a large territory, such as a continent.

    During 2014 careful review, checking out and improvement of the NG DB took place as well redaction of used geochemical and geological terminology; all concentrations were represented as dimensionless values, comments to the NG DB were prepared and in March 2015 the NG DB was ready to be opened for geochemical community (see <http://deepcarbon.net/dco_datasets>).

    The second aim of the project envisaged Review of available scientific literature, related to using noble gases as traces of HC materials.  At present the manuscript is completed: this is a large paper including Text (37000 words), 1 Table, 31 Figures, Glossary and 150 references.  The Review presents not merely the known published issues, but also new ideas and interpretations.  It also includes Russian contributions, poorly known to international geochemical community.  The Review should be submitted later in this summer (2015).   For example, it is shown, that the “average” (statistically representative) HC fields, situated at different tectonic settings (i.e., ancient plates with 300 to 800 Myr old basement; young plated with less than 300 Myr old basement; and presently mobile belts, island arcs and other tectonically active regions) contain much more radiogenic noble gas species compared with those produced in situ by radioactive decay within HC bearing rocks during their sedimentation ages.  Hence, HC fields may be considered as samplers of noble gases from rather large volumes of ground waters (degassed in the course of HC field production), and quantitative estimates of the volume ratio of HC source rocks over HC field rocks are possible.  These ratios are generally vary from 10th to 100th.  Moreover, NG abundances in HC fields also allow the time interval between ground water recharge and degassing to be constrained.  These time intervals are very long and quite similar to the sedimentation ages of HC field rocks at different tectonic settings, thus highlighting the ancient apparent ages of ground waters participating in HC field formation.  Correspondingly, these relationships indicate young ages of the HC materials compared with ages of the sediments in which HCs had been transferred and which contain them at present. 

    Songliao Basin Drilling

    Gas from the deep earth, including biotic and abiotic hydrocarbons and other inorganic gases, is of much significance both in the exploration of deep energy and our understanding of the deep world. On the basis of traditional viewpoint, the exorbitantly temperature in the deep earth may resulting in the over-maturity of organic matter which then lose the ability to generate oil and gas. However recent researches have proved that this concept is actually outdated. Researchers have attested that organic matters can remain stable even under the high temperature conditions in the deep, and a lot of deep reservoirs have been found worldwide. Confirmed by the experimental results, it has been shown that pressure can effectively inhibit the maturation of organic matters in source rock. In addition to the degradation of organic matters, hydrocarbons can also be generated by inorganic matters such as carbon dioxide through Fischer - Tropsch reaction.

    Songliao Basin, as China’s largest oil-producing region, has a long history of petroleum exploitation. It has a clear two-layer structure and was formed by rifting and down-warping. According to the seismic data, a thin layer of low-velocity zone exists at the bottom of the basin, showing extremely high geothermal flux, and can be inferred as a fluid-phase magma chamber. An effort led by Prof. Chengshan Wang is focused on the deep drilling activity in the basin.

    Analysis of the chemical constituents and isotopes of the gas sample collected from the SK-Ⅱdrilling process has been done to show the origin of the gas. Through the analysis, it’s obvious that the carbon isotope ratios of gas within some regions of Songliao Basin significantly distribute in reverse order, while the hydrogen isotope ratios show positive sequence distribution. The combination of carbon, hydrogen and helium isotope is a powerful evidence to prove that these gases are certainly abiogenic rather than organic origin. And at the same time, it reveals the fact that mantle fluid has affected the element composition of hydrocarbon in the source rock of Songliao Basin. The role of the magma chamber at the bottom of the basin has also been figured out by studying the carbon dioxide found in the nature gas well which has the character of magma origin.

    The SK-Ⅱ drilling project conducted in the Songliao Basin has successfully revealed the existence of large-scale, economic abiogenic gas resources, and will undoubtedly benefit the society and economy. SK-Ⅱand its correlative project will become a model example to the exploration of abiogenic gas reservoirs all over the world.

    Continental Serpentinization Systems

    This effort led by Giuseppe Etiope of INGV involved an assessment of abiotic methane production temperature in continental serpentinization systems based on CH4 isotopologue geothermometry and geologic data.

    In July-August 2013 the specifications of gas sampling and storage for isotopologue analyses were defined in agreement with Caltech and MIT laboratories. Technical meetings were organized between Caltech lab (Eiler) and GasConsult Int. (Schoell). In the period September-November 2013, three sets of gas and water samples were collected from seeps and springs in continental serpentinization sites in:

    • Greece (Othrys ophiolite), field work by INGV (Etiope).
    • Portugal (Cabeco de Vide intrusive complex), field work by INGV (Etiope).
    • Turkey (Chimaera seep in Tekirova ophiolite), field work by Istanbul University (Hosgormez).

     

    Samples were sent to the project partners of Caltech (J. Eiler lab; Greek, Portuguese and Turkish samples) and MIT (S. Ono lab; Turkish samples) for stable C and H isotopic and CH4 isotopologue analyses.

    The second year was focused on a new sampling of gas in Italy (Genova hyperalkaline spings) and to the follow-up of the analyses performed by Caltech and MIT and interpretation of the results. The new samples from Italy were sent to Caltech in June 2014. Unfortunately no isotopologue data, regarding the samples from Greece, Portugal and Italy have been received from Caltech so far, despite repeated requests. Only a generic information about the estimated temperature of formation of methane of the Chimaera seep was received. E-mail correspondence with Caltech was then focused on the isotopologue data of Chimaera gas. Their results suggest a quite high temperature of formation of CH4 (>200 °C) which is in contrast with the geologic setting of Chimaera and with the results obtained by MIT, i.e. around 130°C. Caltech and MIT analysed exactly the same gas, collected from the same seep, the same day. There was no follow up on the possible explanations of this difference in the results, and on how Caltech wants to address this fact.

    During a meeting at the AGU conference in San Francisco (December 2014) INGV and MIT decided to perform additional analyses and elaborate the existing data considering that Chimaera gas is not totally abiotic (up to 20% of gas may be thermogenic as suggested in Etiope et al 2011; EPSL). Accordingly, in February 2015 a new set of gas samples from Chimaera was collected and planned to be sent to MIT. Unfortunately MIT informed that the laboratory was not operative due to technical problems caused by the low winter temperatures in Boston. Dr. Ono communicated that the analyses could not be done until autumn 2015. It was decided, then, to contact Ed Young at UCLA; he accepted to analyze the Chimaera gas with his new Panorama system. The samples are now in his laboratory, waiting for analyses.

    The second year was also aimed at the sampling of high temperature gas for isotopologue analyses. Gas was collected at geothermal-volcanic systems of Nisyros (Greece), Pantelleria and Vulcano (Italy) by Jens Fiebig (Frankfurt University) and the samples have been sent to Caltech laboratory (John Eiler). Three fumarolic gas samples from Nisyros and Pantelleria were sent to John Eiler's lab for clumped isotope analysis on methane. For this purpose, Nisyros was sampled in June 2013 by Jens Fiebig.  At the end of May 2015 John Eiler stated that these samples could not have been measured so far. He expects them to be analyzed by the end of this summer the latest. In addition, the INGV team elected to invest part of their DCO funds to set up a technique for hydrogen isotope analysis of nmol quantities of methane. The technique works fine now and has been applied to determine the hydrogen isotopic composition of methane discharging from the Plegrean Fields, Vesuvio and Ischia.

    Finally, the rest of the DCO funds will be used to support hydrocarbon work on Icelandic fumaroles. It is the ultimate aim of this field campaign to determine the C- and H isotopic composition of the n-alkanes as well as the clumped isotopic composition of methane contained in these fumaroles. Icelandic volcanic gaseous emissions exhibit a large range of 3He/4He ratios, indicating that He derives both from the upper and lower mantle. Analyzing the C- and H-isotopic composition of the n-alkanes as well as the clumped isotopic composition of the methane might help to unravel whether the mantle contributes to overall methane generation underneath Iceland. This work will be part of a close collaboration between Jens Fiebig, Andri Stefansson (University of Reykjavik), Shuhei Ono (MIT) and David Hilton (Scripps). For logistic reasons the sampling cannot be performed by the end of the project; it will be held in August-September 2015.

    Oceanic Lithosphere Systems

    The group of Gretchen Früh-Green at the ETH Zurich focused their research on sources and sinks of carbon and processes of fluid-rock interaction in modern and ancient rocks of the oceanic lithosphere. This includes comparative field studies of geochemical and microbial processes during serpentinization and the precipitation of carbonate (±brucite) in two high alkaline, ultramafic environments: the active marine Lost City hydrothermal system (MAR, 30°N), and high alkaline, Ca-OH springs associated with present-day serpentinization and carbonate deposits in the Voltri Massif (Liguria, N. Italy). An additional goal was to combine radiocarbon with stable isotope studies to determine whether the source of carbon for high concentrations of organic acids (formate, acetate) in the Lost City fluids is mantle-derived or seawater bicarbonate. This involved considerable method development. Lipid biomarkers that are diagnostic of methanogens and sulfate reducers were isolated and their 14C content determined. Stable isotope and radiocarbon analyses of both formate and the limited biomarkers yielded F14C signatures that reflect a mixed carbon source dominated by mantle carbon and suggest that the dominant micro-organisms living in the Lost City chimneys consumes an abiotically formed organic molecule. Analyses of methane from alkaline springs in the Voltri Massif, Liguria yielded signatures that were radiocarbon free and which substantiates a mantle carbon origin of methane in present-day serpentinization systems.

    In addition, investigations using Scanning Electron Microscopy (SEM) highlight the close association between microbial biofilms, calcium carbonate, and brucite. In some instances, brucite forms long ropes that may be attributed to microbially-influenced precipitation. In other instances, aragonite appears to precipitate first and then is covered by brucite. Dense biofilms are intimately linked with the growing minerals. These studies have involved collaborations with Susan Lang (ETH), Marvin Lilley (Univ. Washington), Matt Schrenk (DCO-Deep Life, E. Carolina Univ.), William Brazelton (now at Univ. Utah), Stefano Bernasconi (ETH) and Tomaso Bontognali (ETH), many of which are new to DCO. Results have been presented at Goldschmidt 2013, Fall AGU 2013, Fall 2014 and Goldschmidt 2014.

    G. Früh-Green has also been strongly involved in the planning and technical developments to core and seal 10 sites across the Atlantis Massif during IODP Expedition 357, which will take place Oct.–Dec. 2015 (co-chief scientists Gretchen Früh-Green, ETH Zürich; Beth Orcutt, Bigelow Laboratory for Ocean Sciences; http://www.eso.ecord.org/expeditions/357/357.php). A major scientific goal for the expedition is to better understand the role of serpentinization of mantle rocks in driving hydrothermal systems, in sustaining microbial communities, and in the sequestration of carbon in ultramafic rocks.

    Experimental work at ETH has also been carried out in collaboration with Marvin Lilley (academic guest at ETH from Aug-Dec, 2013; May-June, 2014). Construction and testing of a custom-designed cryrogenic inlet system to concentrate gaseous phases and measure compound-specific isotopes by continuous-flow mass spectrometry has been completed. Measurements can now be made on fluids with a minimum concentration of 150nl CH4. ETH researchers are in the process of using this inlet system to measure C-O-H fluids from experimental capsules.

    A new project (with leveraging from DCO) has been submitted to the Swiss National Science Foundations (SNSF) (planned start date: 1 Nov 2015) to combine microstructural studies of fluid and reaction pathways with in-situ probing to constrain microfracturing networks and heterogeneities of fluid-peridotite interactions drill cores from the Atlantis Massif (IODP Exp. 357) and from active serpentinization sites in Oman (ICDP drilling project with DCO funding). These data will be used to quantify mineralogical and chemical changes that control H2 production and the speciation, release or consumption of carbon during progressive serpentinization. Raman microspectroscopy, standard stable isotope analyses of bulk samples and in-situ ion microprobe analyses (SIMS and NanoSIMS) will be used to investigate the nature, composition and distribution of reduced carbon phases in rocks from the upper oceanic mantle, and to distinguish abiotic from biotic carbon in serpentinites. This project will also involve new collaborations within the DCO with Bénédicte Ménez (IPGP).

    The IPGP team members led by Benedicte Menez focused on characterizing reactions and carbon transfers at the macro- and micro-environment scales in natural samples from the oceanic lithosphere.

    They determined the identity of the absorbed or condensed organic matter (OM) accumulated in abyssal serpentinites and associated venting systems, and the amount of OM stored in the oceanic crust and its composition. The approach was based on micropetrographic investigation of OM in equilibrium with low-T phases. They used Raman microimaging, SEM and TEM whose results will be ultimately combined with synchrotron experiment to explore metal-OM coupling and distribution at micro to nano scale (D. Brunelli, M. Sforna). A strong collaboration was formally established with F. Jamme and M. Réfrégiers (synchrotron SOLEIL, France) with notably a co-funded 2-years postdoc that led to the development a multimodal approach involving single-or two-photon spectroscopy, deep UV microscopy and tofSIMS suited for oceanic serpentinites to shed light on the C and N speciation (C. Pisapia, B. Ménez) The organic carbon trapped in mantle-derived rocks likely represents a fraction not yet taken into count in the deep carbon cycle (papers in progress). Work focused on samples from present-day ridges (<1 Ma) and old mantle batches obducted in ophiolitic terrains (130-150 Ma) to reveal the presence and persistence of condensed organic matter in such systems. For the ridge sites sample suites were investigated from the Southwest Indian Ridge (Smoothseafloor region), the Mid Atlantic Ridge (4-6°N and Atlantis Massif) (papers in progress).

    IPGP team members also performed studies of the carbonation reactions of serpentinites sampled along active detachment systems located at the South Western Indian Ridge (SWIR, 64°35'E ) investigated during the SMOOTHSEAFLOOR cruise (PI: D. Sauter and M. Cannat). In this framework M. Cannat and I. Martinez supervised a Master degree student from IPGP (V. Payré) to carefully study the carbonate-serpentine contacts in brecciated samples. Contacts between carbonate and serpentine are being studied on FIB thin sections. Moreover, to better constrain T and fluid composition, the first isotopologue measurements of ∆47 will be performed during the summer of 2015.

    Geological observations at slow-spreading ridges are critical to understand water-rock interactions through the observation of both the alteration in sampled rocks, and the distribution and nature of hydrothermal activity. Oceanic detachment faults are of particular interest in that a) tectonic processes that expose deep seated rocks from the lower crust and upper mantle at the seafloor, b) hydrothermal activity appears to be pervasive at these sites, often in ultramafic host-rocks, and c) the exhumed materials systematically record a long history of fluid-rock interactions ranging from low to high temperatures. J. Escartin’s initial work focused on the Rainbow hydrothermal site (see Andreani et al., 2014) to obtain an overview of the geology of the area and understand its tectonic setting.  This geological and tectonic synthesis set the ground for the 2015 Rainbow  Workshop (June 2015), led by M. Andreani from the Lyon University, to coordinate efforts for a drilling proposal at this site, and drafting proposals for additional cruises (France, USA) to study further this site. During Year 1 J. Escartin (IPGP) also led a major oceanographic cruise (ODEMAR 2013) on the 13°20’N and 13°30’N detachments along the Mid-Atlantic Ridge during which they conducted extensive geological observations and sampling of the detachment fault surface using ROVs, complemented with high-resolution geophysical surveys with AUVs. The scientific exploitation of cruise data and samples is in progress, and a sizeable part of these are part of an on-going PhD Thesis by D. Bonnemains. who carried out systematic petrographic studies on thin sections, microstructural analyses with electron microscopy, and major and trace element analyses in addition to isotope geochemistry, largely funded by DCO. These results are being interpreted, integrated, and analyzed by D. Bonnemains, whose thesis is expected to be completed by Sep. 2016.

    IPGP also published the results obtained on the hydrothermal field of Prony (New Caledonia; HYDROPRONY cruise PI: B. Pelletier IRD Nouméa) through 4 publications (Quéméneur et al. 2014; Monnin et al., 2014; Pisapia et al., 2015; Postec et al., 2015). These first four papers respectively describe the hydrothermal fluid chemistry, the microbial ecology and the geobiology along with the mineralogy. This system corresponds to an exciting example of hyperalkaline and H2/CH4-rich hydrothermal field sustained by serpentinization reactions. It is the closest known analog of the Lost City Hydrothermal Field close to the Mid-Atlantic Ridge, and observations at the micrometric scale has allowed C. Pisapia, B. Ménez and E. Gérard to propose a new model of Subsurface Lithotrophic Microbial Ecosystems that exist and persist independently from photosynthesis reaction (Pisapia et al., 2015).  These efforts were the results of collaboration with an interdisciplinary research team affiliated with the Institute of Research for Development (IRD, Nouméa, New Caledonia), the Mediterranean Institute of Oceanography (MIO, Marseille, France), the CNRS-GET lab from Toulouse University (France), the Institut de Physique du Globe de Paris (IPGP) and the Institut de Minéralogie et de Physique des Milieux Condensés (IMPMC, Paris, France).

    New measurements defined the fate of carbon and nutrients during shallow melting of the upper mantle along spreading ridges in relation to mantle source heterogeneities. Notably D. Brunelli conducted major and trace element analyses of relic primary minerals of a large collection of mantle peridotites. Sample collection is from eastern SWIR (SMOOTHSEAFLOOR), central SWIR (Andrew Bain) and western SWIR (Bouvet Triple Junction). Modelling for the melting, and melt extraction processes was carried out (paper in progress).

    Ocean Hydrothermal Vents

    Max Coleman from Caltech/NASA used DCO funds to participate in the Cayman hydrothermal vent cruise of 2013. From this effort he was able to track the food chain at two neighboring hydrothermal vent sites 20 km apart but at depths of 2300 m and nearly 5000 m. He was able to show that some essential fatty acid lipids, previously thought only to be produced by organisms in the photic zone were synthesized at depth by the chemosynthetic-based ecosystem in the vicinity of the event site. He further observed unexpected dietary habits of part of the extensive shrimp population, previously thought to be solely living off chemosynthetic bacteria but in fact are carnivorous, or even cannibalistic. The key finding for the carbon cycle is that oxidation of sulfide from the vent by chemo-synthetic bacteria produces a sink for dissolved CO2 and is converted into carbohydrate.  This serves as the basis of the extensive ecosystem and provides biomass, some of which is buried within the sediment. The amount of trace carbon in the basalts was greater than expected, and comprised both acid soluble and acid insoluble fractions, the former believed to be carbonate resulting from interaction with ocean water. Further work on the speciation of the particular carbon forms is still needed.

    1B. Sherwood Lollar also receives DCO funding from the Field Studies project led by Peter Kelemen

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