Hydrothermal Hydrocarbons

Stanley B. Keith¹ and Monte M. Swan^2
1 MagmaChem, LLC, P. O. Box 672, Sonoita, Arizona, USA, 85637
² MagmaChem, LLC, 7072 Singing Springs, Evergreen, Colorado, USA, 80439

Hydrocarbon origin theories have focused on: 1) generation of gas and crude oil via burial diagenesis of biogenic, organic-rich sedimentary rocks, and 2) abiogenic hydrocarbon generation in the mantle. We suggest a third possibility--the generation of methane and heavier hydrocarbons through reactions that occur during cooling, fractionation, and deposition of dolomitic carbonates, metal-rich black shales, and other minerals from hydrothermal metagenic fluids. These fluids are proposed to be the product of serpentinization of carbon-rich peridotites under hydrogen-rich, reduced conditions. The association of hydrothermal ore genesis and accessory hydrocarbon has been known for years in economic metal deposits (for example, Gize, 1999). Recent application of mineral industry research to petroleum geology suggests that petroleum accumulations could be considered, at least in part, mineral deposits—products of hydrothermal, geochemically-zoned fluid plumes that possess identifiable paragenetic sequences (Keith and Swan, 2005).

Direct evidence for hydrothermal hydrocarbons continues to mount. Some of the more relevant observations include:

1. Hydrothermal dolomite (HTD) not only hosts hydrocarbons, but has trapped hydrocarbons during its deposition under hot hydrothermal conditions (100-200 C) (for example Hulen and others, 1994 at Railroad Valley, Nevada). HTD is associated with large oil and gas accumulations including the supergiant Ghawar field in Saudi Arabia (Cantrell and others, 2001).
2. Geochemistry of hydrocarbons, experimental work, and mass-balance calculations have identified the fluids that produce HTD as hot, strongly-reduced, hydrocarbon-rich chloride and/or bicarbonate brines containing elements exotic to basins such as Mg, Fe, Ni, V, Se, Co, and Zn. Indeed, many oil field brines may represent the original hydrothermal carrier fluid for reservoir hydrocarbons.
3. Virtually all oil is now known to contain nanodiamond particles and their diamondoid overgrowths. Nanodiamond presence strongly suggests a high-pressure, high-temperature origin at some point in the generation, migration, and deposition of the hydrocarbon (Dahl and others, 2003 a and b).
4. Thermogenic abiogenic low-C number hydrocarbon gases (mainly methane) have been experimentally produced under hydrothermal conditions that simulate serpentinization of a peridotite source (Berndt and others, 1996; Horita and Berndt, 1999). Ultrathermogenic methane has also been produced experimentally by reacting magnetite, calcite, and water in a diamond anvil high-pressure apparatus under mantle pressures and temperatures (Science News, 2004).
5. Oil has been shown to produce copious amounts of catalytic gas by heating above 130 C in the presence of native metals such as Fe, Ni, and Co. The rates of reaction are geologically instantaneous and easily fit within the lifespan of a hydrothermal plume system (Mango, and others, 1994).
6. Humans have been unintentionally modeling and producing gasoline under hydrothermal hydrocarbon conditions for decades. Starting in the Second World War industrial scale ‘hydrothermal’ gasolines have been produced by injecting hydrogen into hot carbon oxides produced from pyrolysis of coal cokes and subsequently cooling and condensing the hydrothermal mixture across a metalliferous (native metal) catalytic interface (Fischer-Tropsch process, see Szatmari, 1989).
7. Large methane-charged hydrothermal seepages have been recently discovered in oceanic transform environments such as the Lost City ‘white smoker’ field in the central Atlantic (Kelley and others, 2001, Fruh-Green, 2004). These seepage phenomena provide evidence that serpentine-sourced, crustal-scale hydrocarbon systems may breach the lithosphere. Where they do so, at a subaqueous interface, they may furnish inorganic hydrocarbon, metal, and other chemical exhalative material for black shale accumulations. Indeed, hydrocarbons generated by this process may still be replenishing producing reservoirs (for example, the Eugene Island 300 reservoir in the deep Gulf of Mexico).

An important corollary feature of the last point is that hydrocarbon-enriched hydrothermal seepages into the lithosphere-hydrosphere interface provide a vital energy/nutrient source that attracts and sustains the biosphere component. Indeed, chemosynthesis in the presence of metal at hydrothermal vent sites like Lost Cities may have contributed to polymerization and production of large organic molecules (e.g. DNA) necessary to spawn life very early in the planet’s history. Continued interaction of the biosphere with the hydrocarbon-enriched hydrothermal nutrient sites may have led to its rapid evolution, expansion, and preservation (via mineral replacement at seepage sites) at critical thresholds during oxidation at the earth’s hydrosphere-biosphere system (for example the Burgess shale in British Columbia).

In this sense, inorganic hydrocarbon and organic hydrocarbon sources have inexorably, inevitably, and continuously co-mingled since the planet’s inception. In effect, the biosphere has been consuming inorganic carbon for over four billion years. Once formed, the black shale strata may become source rocks for generation of conventional hydrocarbons. However, we believe the origination of such an environment has more to do with the initial importation of hydrothermal hydrocarbon products generated from serpentinization of distinct types of carbon-rich peridotite sources in the inner planet. The serpentinization of peridotite may take place within any number of tectonic settings, including sedimentary burial or orogenic thrust loading, alteration in an ocean basin rift environment in the presence of brines, or flat subduction. A generic model for hydrothermal hydrocarbon that incorporates all of the foregoing observations is presented below (Figure 1).

Carbon-rich peridotite at green schist facies conditions is initially with low pH, chloride and bicarbonate brines generated from metagenic devolatization of oceanic crust at the zeolite facies-green schist facies grade change. Xenocrystic nanodiamonds particulates from the original peridotite are incorporated into a hydrogen and methane-charged hydrothermal brine product, which leaves the serpentine source under high geopressure due to the great volume expansion of the serpentine relative to its peridotite precursor. The methane charged hydrothermal brine products ascend through a reduced crust using deep-seated fracture conduits. The conduit system typically experiences a combination strike-slip or reversal/thrust-slip kinematics driven by orogenic horizontal compression. Where the fluids encounter shelf limestones near the base of basin cover sequences. Extensive replacement reactions occur in which large volumes of hydrothermal dolomite are formed. Because this reaction uses a large amount of oxygen to make solid-state dolomite, the residual fluids become even more reduced and additional hydrocarbons are formed—especially where metal-rich sulfides are precipitated.

The hydrocarbon-charged plume continues to ascend through the basin where it may deposit oil and gas in appropriate stratigraphic and/or structural traps. Inevitably, the hydrothermal hydrocarbon-charged plume ‘exits’ the lithosphere as metalliferous, hydrocarbon enriched seep(s), which may become exhalatively incorporated in black shale orogenic basins above the deep-seated conduit system. The black shales provide stratigraphic time lines that date the emplacement of the petroleum system. It is in these black shales that the hydrocarbon plume interacts with and co-mingles with the earth’s biosphere--probably a fundamental source of energy and nutrient. Where liquid state petroleums are formed within the crustal column affected by the hydrocarbon-charged hydrothermal plume, nanodiamonds which survive the depositional process, are co-deposited with the petroleum and provide a tracer back to the diamond-stable peridotite source. Diamonoid overgrowths now reflect the thermal regime present during oil formation with higher-C number diamondoids indicating more oxidative, hot formational conditions. Hydrothermal hydrocarbons have formed in this way since early earth history. Indeed, hydrothermal hydrocarbon continues to actively form and replenish (for example, the aforementioned Eugene Island 300 reservoir).

If the hydrothermal hydrocarbon model is viable, it will engender new exploration strategies, with applications from regional to reservoir scale. Petroleum systems will have to be viewed as crustal-scale features with a geology extending from the serpentinized peridotitic source to the seepage sites at the top of the crust. Petroleum geology is much larger than the basins within which petroleum has been traditionally found. The petroleum geologist of the future will need to acquire new skill sets derived from igneous and metamorphic petrology as-well-as economic geology of metal deposits. Hard rock geology and soft rock geology will no longer exist as separate disciplines as geologists view basins from the basement up.

For example, stratigraphic traps in cratonic cover sequences above basement peridotitic sources could become exploration targets. And, because a given hydrothermal plume fluid-flow pathway is much greater in extent than the fractionated hydrocarbon zones, it may be possible to predict the position of hydrocarbon-rich hydrothermal plumes (i.e., potential reservoirs) by examining more distal parts of the plume. In other words, because the fractionation pattern is regular and predictable, the pattern of hydrothermal fractionation may be predictable on regional, play, and prospect scales, and it may be possible to identify the most likely location of sweet spots. The concept of serpentinite hydrocarbon sources may helps identify new exploration leads through its magnetic-high, gravity-low geophysical signature. Identifying the migration path of fluids generated by serpentinization may identify plays. The associated reservoir architecture may be delineated through geokinematic analysis of structure combined with vectoring of HTD and black shale geochemical mineralization.

New exploration techniques will be required. Integrated, three-dimensional, fluid-flow fractionation models of target reservoir possibilities can be generated using:

• detailed mineralogical data such as down hole mineralogical studies that examine the geographic distribution of secondary clay, feldspar, quartz, and carbonate deposition during hydrothermal diagenesis.
• geochemical data such as multi-element down-hole and surface geochemical characterizations including both hydrocarbons and metals.
• remote sensing data such as satellite imagery including identification of bright spots and infrared thermal patterns, digital elevation and low-altitude stereo-paired photographic interpretation to identify basement structure that integrate downward into the peridotite sources in the deep basement.
• geophysical data such as seismic interpretation, induced electrokinetic follow-up of more regional gravity and magnetic studies (which identify a deep-seated serpentinite source), and identification of seismic attributes associated with reservoir rock properties whenever possible.
• geological data such as detailed geologic surface mapping at various scales, and regional strato-tectonic analysis.

Because some of these exploration techniques are more familiar to the metals exploration industry than they are to the petroleum exploration industry (for example, the multi-element geochemical techniques), a partnership between experts in both sets of disciplines will be highly effective in developing new exploration techniques. Ultimately, the hydrothermal hydrocarbon point of view offers a broader set of exciting exploration opportunities. New petroleum resources (especially thermogenic gas and light, low-sulfur oil) may exist in any number of trap configurations beneath and between know hydrocarbon accumulations and the underlying deep seated serpentinite sources.

REFERENCES

Berndt, M.E., Allen, D.E., and Seyfried Jr., W.E., 1996 Reduction of CO2 During Serpentinization of Olivine at 300 C and 500 Bar: Geology, April 1996; v.24, n.4; pp.351-354.

Cantrell, D.L., Swart, P.K., Handford, R.C., Kendall, C.G., and Westphal, H., 2001, Geology and Production Significance of Dolomite, Arab-D Reservoir, Ghwar Field, Saudi Arabia: GeoArabia (Manama), Gulf Petrink in Bahrain, Manama, Bahrain, v.6, n.1, p. 45-60.

Dahl, J.P., Liv, D.G., and Carlson, M.K., 2003, Isolation and Structure of Higher Diamondoids, Nonometer-Sized Diamond Molecules: Science, v.229, p.96-99

Dahl, J.P. and many others, 2003, Isolation and Structural Proof of the Large Diamond Molecule, Cydohexamantane (C26H30): Angew. Chem. Int. Ed., v.42, p.2040-2044.

Fruh-Green, G., Connolly, J.A.D., Kelly, D.S., Groberty, B., and Pias, A., 2004, Serpentinization of Oceanic Peridotites: Implications for Geochemical Cycles and Biological Activity: Chapter 8 in Oceanic Serpentinization: AGU, p.119-136.

Gize, A.P., 1999, Organic Alterations in Hydrothermal Sulfide Ore Deposits: Economic Geology, v. 94, n.7, November, 1999., pp. 967-979.

Horital, J., and Berndt, M.E., 1999, Abiogenic Methane Formation and Isotopic Fractionation under Hydrothermal Conditions: Science, v. 285, p.1055-1057.

Hulen, J.B., Goff, F., Ross, J.R., Bortz, L.C. and Bereskin, S.R., Geology and Geothermal Origin of Grant Canyon and Bacon Flat Oil Fields, Railroad Valley, Nevada: American Association of Petroleum Geologists Bulletin, v.78, p.596-623.

Keith, S.B. and Swan, M.M., 2005, Unpublished Research and MagmaChem Company.

Kelly, D.S., and many others, 2001, An Off-Axis Hydrothermal Vent Field Near the Mid-Atlantic Ridge at 30 Degrees North: Nature, v. 412, p.145-149.

Kenney, V.G., Kutcherov, N.A., Rendeliani, V.A., and Alekseev., 2002, The Evolution of Multicomponent Systems at High Pressures: VI. The Thermodynamic Stability of the Hydrogen-Carbon System: The Genesis of Hydrocarbons and the Origin of Petroleum, Proceedings of the National Academy of Sciences, 99, 10976-10981.

Mango, F.D., Hightower, J.W., and James, A.T. 1994 Role of Transition-Metal Catalysis in the Formation of Natural Gas: Nature, 368, pp.536-538.

Science News, 2004, Deep Squeeze: Experiments Point to Methane in Earth’s Mantle: Science News—This Week, September 25, 2004, v.266.

Szatmari, P., 1989, Petroleum Formation by Fisher-Tropsch Synthesis in Plate Tectonics: American Association of Petroleum Geologists Bulletin, v.73, n.8 (August, 1989), pp.989-998.

Figure 1. Conceptual Model for Generation of Hydrothermal Hydrocarbons During Serpentinization of Peridotitic Source and Subsequent Hydrothermal Dolomitization and Exhalative Block Shale Formation.