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K.A. Kvenvolden

Publications and source records attributed to K.A. Kvenvolden.

At least 37 records · Page 2Linked to original sources

Chemistry, isotopic composition, and origin of a methane-hydrogen sulfide hydrate at the Cascadia subduction zone

Although the presence of extensive gas hydrate on the Cascadia margin, offshore from the western U.S. and Canada, has been inferred from marine seismic records and pore water chemistry, solid gas hydrate has only been found at one location. At Ocean Drilling Program (ODP) Site 892, offshore from central Oregon, gas hydrate was recovered close to the sediment-water interface at 2–19 m below the seafloor (mbsf) at 670 m water depth. The gas hydrate occurs as elongated platy crystals or crystal aggregates, mostly disseminated irregularly, with higher concentrations occurring in discrete zones, thin layers, and/or veinlets parallel or oblique to the bedding. A 2- to 3-cm thick massive gas hydrate layer, parallel to bedding, was recovered at ∼ 17 mbsf. Gas from a sample of this layer was composed of both CH 4 and H 2 S. This sample is the first mixed-gas hydrate of CH 4 H 2 S documented in ODP; it also contains ethane and minor amounts of CO 2 . Measured temperatures of the recovered core ranged from 2 to −1.8°C and are 6 to 8 degrees lower than in-situ temperatures. These temperature anomalies were caused by the partial dissociation of the CH 4 H 2 S hydrate during recovery without a pressure core sampler.During this dissociation, toxic levels of H 2 S (δ 34 S, +27.4‰) were released. The δ 13 C values of the CH 4 in the gas hydrate, −64.5 to −67.5‰ (PDB) , together with δD values of −197 to −199‰ (SMOW) indicate a primarily microbial source for the CH 4 . The δ 18 O value of the hydrate H 2 O is +2.9‰ (SMOW) , comparable with the experimental fractionation factor for sea-ice. The unusual composition (CH 4 H 2 S) and depth distribution (2–19 mbsf) of this gas hydrate indicate mixing between a methane-rich fluid with a pore fluid enriched in sulfide; at this site the former is advecting along an inclined fault into the active sulfate reduction zone. The facts that the CH 4 H 2 S hydrate is primarily confined to the present day active sulfate reduction zone (2–19 mbsf), and that from here down to the BSR depth (19–68 mbsf) the gas hydrate inferred to exist is a ≥99% CH 4 hydrate, suggest that the mixing of CH 4 and H 2 S is a geologically young process. Because the existence of a mixed CH 4 H 2 S hydrate is indicative of moderate to intense advection of a methane-rich fluid into a near surface active sulfate reduction zone, tectonically active (faulted) margins with organic-rich sediments and moderate to high sedimentation rates are the most likely regions of occurrence. The extension of such a mixed hydrate below the sulfate reduction zone should reflect the time-span of methane advection into the sulfate reduction zone.

Earth and Planetary Science Letters

A primer on the geological occurrence of gas hydrate

This paper is part of the special publication Gas hydrates: relevance to world margin stability and climatic change (eds J.P. Henriet and J. Mienert).Natural gas hydrates occur world-wide in polar regions, usually associated with onshore and offshore permafrost, and in sediment of outer continental and insular margins. The total amount of methane in gas hydrates probably exceeds 1019 g of methane carbon. Three aspects of gas hydrates are important: their fossil fuel resource potential; their role as a submarine geohazard; and their effects on global climate change. Because gas hydrates represent a large amount of methane within 2000 m of the Earth's surface, they are considered to be an unconventional, unproven source of fossil fuel. Because gas hydrates are metastable, changes of pressure and temperature affect their stability. Destabilized gas hydrates beneath the sea floor lead to geological hazards such as submarine slumps and slides, examples of which are found world-wide. Destabilized gas hydrates may also affect climate through the release of methane, a 'greenhouse' gas, which may enhance global warming and be a factor in global climate change.

Geological Society Special Publication

Deep-ocean field test of methane hydrate formation from a remotely operated vehicle

We have observed the process of formation of clathrate hydrates of methane in experiments conducted on the remotely operated vehicle (ROY) Ventana in the deep waters of Monterey Bay. A tank of methane gas, acrylic tubes containing seawater, and seawater plus various types of sediment were carried down on Ventana to a depth of 910 m where methane gas was injected at the base of the acrylic tubes by bubble stream. Prior calculations had shown that the local hydrographic conditions gave an upper limit of 525 m for the P-T boundary defining methane hydrate formation or dissociation at this site, and thus our experiment took place well within the stability range for this reaction to occur. Hydrate formation in free sea-water occurred within minutes as a buoyant mass of translucent hydrate formed at the gas-water interface. In a coarse sand matrix the Filling of the pore spaces with hydrate turned the sand column into a solidified block, which gas pressure soon lifted and ruptured. In a fine-grained black mud the gas flow carved out flow channels, the walls of which became coated and then filled with hydrate in larger discrete masses. Our experiment shows that hydrate formation is rapid in natural seawater, that sediment type strongly influences the patterns of hydrate formation, and that the use of ROV technologies permits the synthesis of large amounts of hydrate material in natural systems under a variety of conditions so that fundamental research on the stability and growth of these substances is possible.

Geology

The nature, distribution, and origin of gas hydrate in the Chile Triple Junction region

A bottom simulating reflector (BSR) is regionally distributed throughout much of the Chile Triple Junction (CTJ) region. Downhole temperature and logging data collected during Ocean Drilling Program (ODP) Leg 141 suggest that the seismic BSR is generated by low seismic velocities associated with the presence of a few percent free gas in a ??? 10 m thick zone just beneath the hydrate-bearing zone. The data also indicate that the temperature and pressure at the BSR best corresponds to the seawater/methane hydrate stability field. The origin of the large amounts of methane required to generate the hydrates is, however, problematic. Low total organic carbon contents and low alkalinities argue against significant in situ biogenic methanogenesis, but additional input from thermogenic sources also appears to be precluded. Increasing thermal gradients, associated with the approach of the spreading ridge system, may have caused the base of the hydrate stability field to migrate 300 m upwards in the sediments. We propose that the upward migration of the base of the stability field has concentrated originally widely dispersed hydrate patches into the more continuous hydrate body we see today. The methane can be concentrated if the gas hydrates can form from dissolved methane, transported into the hydrate zone via diffusion or fluid advection. A strong gradient may exist in dissolved methane concentration across the BSR leading to the steady reabsorbtion of the free gas zone during the upward migration of the BSR even in the absence of fluid advection.

Earth and Planetary Science Letters

Worldwide distribution of subaquatic gas hydrates

Sediments containing natural gas hydrates occur worldwide on continental and insular slopes and rises of active and passive margins, on continental shelves of polar regions, and in deep-water (> 300 m) environments of inland lakes and seas. The potential amount of methane in natural gas hydrates is enormous, with current estimates at about 1019 g of methane carbon. Subaquatic gas hydrates have been recovered in 14 different areas of the world, and geophysical and geochemical evidence for them has been found in 33 other areas. The worldwide distribution of natural gas hydrates is updated here; their global importance to the chemical and physical properties of near-surface subaquatic sediments is affirmed. ?? 1993 Springer-Verlag.

Geo-Marine Letters

Gas hydrates from the continental slope, offshore Sakhalin Island, Okhotsk Sea

Ten gas-vent fields were discovered in the Okhotsk Sea on the northeast continental slope offshore from Sakhalin Island in water depths of 620-1040 m. At one vent field, estimated to be more than 250 m across, gas hydrates, containing mainly microbial methane (??13C = -64.3???), were recovered from subbottom depths of 0.3-1.2 m. The sediment, having lenses and bedded layers of gas hydrate, contained 30-40% hydrate per volume of wet sediment. Although gas hydrates were not recovered at other fields, geochemical and thermal measurements suggest that gas hydrates are present. ?? 1993 Springer-Verlag.

Geo-Marine Letters

Hydrocarbons in oil residues on beaches of islands of Prince William Sound, Alaska

Aliphatic and aromatic hydrocarbons were measured on oil residues from beaches on six islands in Prince William Sound, Alaska. In addition to altered products from the Exxon Valdez oil spill of 1989, we also found, at two widely separated locations, residues that are similar to each other but chemically distinct from the spilled oil. Terpanes, steranes, monoaromatic steranes, and carbon isotopic compositions of total extracts were most useful in correlating the altered products of the spilled oil. These same parameters revealed that the two non-Valdez samples are likely residues of oil originally produced in California. The results indicate that oil residues currently on the beaches of this estuary have at least two quite different origins.

Marine Pollution Bulletin

Possible connection between two Alaskan catastrophes occurring 25 yr apart (1964 and 1989)

On March 24, 1989, the Exxon Valdez supertanker grounded on Bligh Reef, spilling North Slope crude oil into Prince William Sound, Alaska. Tracking the geochemical fate of this spilled oil has revealed, in addition to weathered products from the spill, minor oil residues on beaches from a distinctly different source. By using carbon isotopic compositions of whole-oil residues as a principal method of identification, we found that the δ 13 C values of Exxon Valdez oil (one sample) and its residues (eight samples from six islands) average -29.3 ±0.1‰. In contrast, the non- Exxon Valdez residues (15 samples from 12 localities) have an average δ 13 C value of -23.8 ±0.1‰. This tight distribution of carbon isotopic values suggests a single event to explain the non- Exxon Valdez residues. This event likely was the Great Alaska Earthquake of March 27, 1964. This quake and the subsequent tsunami destroyed asphalt storage facilities at the old Valdez town site, spilling asphalt (δ 13 C = -23.6‰) into Port Valdez fjord. From there the asphalt apparently advanced south into the sound. Thus, the possible connection between two Alaskan catastrophes, separated by 25 yr, is found in the minor oil- like residues that continue to mark the two events on the beaches of Prince William Sound.

Geology

Methane in permafrost - Preliminary results from coring at Fairbanks, Alaska

Permafrost has been suggested as a high-latitude source of methane (a greenhouse gas) during global warming. To begin to assess the magnitude of this source, we have examined the methane content of permafrost in samples from shallow cores (maximum depth, 9.5m) at three sites in Fairbanks, Alaska, where discontinuous permafrost is common. These cores sampled frozen loess, peat, and water (ice) below the active layer. Methane contents of permafrost range from <0.001 to 22.2mg/kg of sample. The highest methane content of 22.2mg/kg was found in association with peat at one site. Silty loess had high methane contents at each site of 6.56, 4.24, and 0.152mg/kg, respectively. Carbon isotopic compositions of the methane (??13C) ranged from -70.8 to -103.9 ???, and hydrogen isotopic compositions of the methane (??D) from -213 to -313 ???, indicating that the methane is microbial in origin. The methane concentrations were used in a one dimensional heat conduction model to predict the amount of methane that will be released from permafrost worldwide over the next 100 years, given two climate change scenarios. Our results indicate that at least 30 years will elapse before melting permafrost releases important amounts of methane; a maximum methane release rate will be about 25 to 30 Tg/yr, assuming that methane is generally distributed in shallow permafrost as observed in our samples.

Conference Paper

Organic markers as source discriminants and sediment transport indicators in south San Francisco Bay, California

Sediment samples from nearshore sites in south San Francisco Bay and from streams flowing into that section of the Bay have been characterized in terms of their content of biogenic and anthropogenic molecular marker compounds. The distributions, input sources, and applicability of these compounds in determining sediment movement are discussed. By means of inspection and multivariate analysis, the compounds were grouped according to probable input sources and the sampling stations according to the relative importance of source contributions. A suite of polycyclic aromatic hydrocarbons (PAHs) dominated by pyrene, fluoranthene and phenanthrene, typical of estuarine environments worldwide, and suites of mature sterane and hopane biomarkers were found to be most suitable as background markers for the Bay. A homologous series of long-chain n-aldehydes (C12-C32) with a strong even-over-odd carbon number dominance in the higher molecular weight range and the ubiquitous n-alkanes (n-C24-C34) with a strong odd-over-even carbon number dominance were utilized as terrigenous markers. Several ratios of these terrigenous and Bay markers were calculated for each station. These ratios and the statistical indicators from the multivariate analysis point toward a strong terrigenous signal in the terminus of South Bay and indicate net directional movement of recently introduced sediment where nontidal currents had been considered to be minimal or nonexistent and tidal currents had been assumed to be dominant.

California

Hydrocarbon gas seeps of the convergent Hikurangi margin, North Island, New Zealand

Two hydrocarbon gas seeps, located about 13 km apart, have distinctive molecular and isotopic compositions. These seeps occur within separate tectonic melange units of narrow parallel trending and structurally complex zones with incorporated upper Cretaceous and Palaeogene passive continental margin deposits which are now compressively deformed and imbricated along the convergent Hikurangi margin of North Island, New Zealand. At Brookby Station within the Coastal High, the seeping hydrocarbon gas has a methane/ethane ratio of 48 and ??13C and ??D values of methane of -45.7 and -188???, respectively (relative to the PDB and SMOW standards). Within the complex core of the Elsthorpe Anticline at Campbell Station seep, gas has a methane/ethane ratio of about 12000, and the methane has ??13C and ??D values of -37.4 and -170???, respectively. The source of the gases cannot be positively identified, but the gases probably originate from the thermal decomposition of organic matter in tectonically disturbed upper Cretaceous and/or lower Tertiary sedimentary rocks of passive margin affinity and reach the surface by migration along thrust faults associated with tectonic melange. The geochemical differences between the two gases may result from differences in burial depths of similar source sediment. ?? 1989.

Marine and Petroleum Geology

Map showing the depth to the base of the deepest ice-bearing permafrost as determined from well logs, North Slope, Alaska

Because gas hydrates from within a limited temperature range, subsurface equilibrium temperature data are necessary to calculate the depth and thickness of the gas-hydrate stability field. Acquiring these data is difficult because drilling activity often disrupts equilibrium temperatures in the subsurface, and a well mush lie undisturbed until thermal equilibrium is reestablished (Lachenbruch and Brewer, 1959). On the North Slope if Akaska, a series of 46 oil and gas exploratory wells, which were considered to be near thermal equilibrium (Lachenbruch and others, 1982; 1987), were surveyed with high-resolution temperature devices (see table 1). However, several thousand other exploratory and production wells have been drilled on the North Slope, and although they do not include temperature profiles, their geophysical logs often allow descrimination between ice-bearing and non-ice-bearing strata. At the outset of this study, the coincidence of the base of ice-bearing strata being near the same depth as the 0 &deg;C isotherm at Prudhoe Bay (Lachenbruch and others, 1982) appeared to offer an opportunity to quickly and inexpensively expand the size of our subsurface temperature data base merely by using well logs to identify the base of the ice-bearing strata.

Alaska

Hydrocarbon gas in sediment of the Southern Pacific Ocean

Methane, ethane, ethene, propane, and propene are common hydrocarbon gases in near-surface sediment from offshore areas in the southern Pacific Ocean near Papua New Guinea, the Solomon Islands, Vanuatu, Tonga, New Zealand, and Antarctica. Sea floor sites for sampling of sediment were selected on the basis of anomalies in marine seismic records, and the samples were intentionally biased toward finding possible thermogenic hydrocarbon gases. In none of the areas, however, were thermogenic hydrocarbons clearly identified. The hydrocarbon gases that were found appear to be mainly the products of in situ microbial processes. ?? 1988 Springer-Verlag New York Inc.

Geo-Marine Letters