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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
USGS1999

PAH refractory index as a source discriminant of hydrocarbon input from crude oil and coal in Prince William Sound, Alaska

Geochemical correlation and differentiation of hydrocarbons from crude oils and coals is difficult. The complex mixture of the hydrocarbon constituents and the dynamic nature of these constituents in the environment as they weather contribute to this difficulty A new parameter, the polycyclic aromatic hydrocarbon (PAH) refractory index, is defined here to help in this correlation. The PAH refractory index is a ratio of two of the most refractory constituents of most crude oils, namely triaromatic steranes and monomethylchrysenes. These are among the most persistent compounds in oil after deposition in the environment and thus retain reliably the signature of the original petroleum input. This index is utilized in Prince William Sound (PWS) to differentiate three different oils, as well as to provide evidence that coal, not oil, is the dominant source of the PAHs which are prominent constituents of marine sediments from PWS and the Gulf of Alaska.Geochemical correlation and differentiation of hydrocarbons from crude oils and coals is difficult. The complex mixture of the hydrocarbon constituents and the dynamic nature of these constituents in the environment as they weather contribute to this difficulty. A new parameter, the polycyclic aromatic hydrocarbon (PAH) refractory index, is defined here to help in this correlation. The PAH refractory index is a ratio of two of the most refractory constituents of most crude oils, namely triaromatic steranes and monomethylchrysenes. These are among the most persistent compounds in oil after deposition in the environment and thus retain reliably the signature of the original petroleum input. This index is utilized in Prince William Sound (PWS) to differentiate three different oils, as well as to provide evidence that coal, not oil, is the dominant source of the PAHs which are prominent constituents of marine sediments from PWS and the Gulf of Alaska.

Conference Paper↗
USGS1999

A record of hydrocarbon input to San Francisco Bay as traced by biomarker profiles in surface sediment and sediment cores

San Francisco Bay is one of the world's largest urbanized estuarine systems. Its water and sediment receive organic input from a wide variety of sources; much of this organic material is anthropogenically derived. To document the spatial and historical record of the organic contaminant input, surficial sediment from 17 sites throughout San Francisco Bay and sediment cores from two locations Richardson Bay and San Pablo Bay were analyzed for biomarker constituents. Biomarkers, that is, 'molecular fossils', primarily hopanes, steranes, and n-alkanes, provide information on anthropogenic contamination, especially that related to petrogenic sources, as well as on recent input of biogenic material. The biomarker parameters from the surficial sediment and the upper horizons of the cores show a dominance of anthropogenic input, whereas the biomarker profiles at the lower horizons of the cores indicate primarily biogenic input. In the Richardson Bay core the gradual upcore transition from lower maturity background organics to a dominance of anthropogenic contamination occurred about 70-100 years ago and corresponds to the industrial development of the San Francisco Bay area. In San Pablo Bay, the transition was very abrupt, reflecting the complex depositional history of the area. This sharp transition, perhaps indicating a depositional hiatus or erosional period, dated at pre-1952, is clearly visible. Below, the hiatus the biomarker parameters are immature; above, they are mature and show an anthropogenic overlay. Higher concentrations of terrigenous n-alkanes in the upper horizons in this core are indicative of an increase in terrigenous organic matter input in San Pablo Bay, possibly a result of water diversion projects and changes in the fresh water flow into the Bay from the Delta. Alternatively, it could reflect a dilution of organic material in the lower core sections with hydraulic mining debris.

California↗
USGS1998

Natural hydrocarbon background in benthic sediments of Prince William Sound, Alaska: Oil vs coal

The source of the background hydrocarbons in benthic sediments of Prince William Sound (PWS), AK, where the 1989 Exxon Valdez oil spill (EVOS) occurred, has been ascribed to oil seeps in coastal areas of the Gulf of Alaska (GOA). We present evidence that coal is a more plausible source, including (i) high concentrations of total PAH (TPAH), between 1670 and 3070 ng/g, in continental shelf sediments adjacent to the coastal region containing extensive coal deposits; (ii) PAH composition patterns of sediments along with predictive models that are consistent with coal but not oil; (iii) low ratios (<0.2) of triaromatic steranes to methylchrysenes found in sediments and coals, contrasting with the high ratios (11 and 13) found in seep oil; and (iv) bioaccumulation of PAH in salmon collected within 100 m of the Katalla oil seeps but not in filter-feeding mussels collected near oilfield drainages 9 km from the seeps, indicating negligible transport of bioavailable PAH from Katalla seeps to the GOA. In contrast with oil, PAH in coal are not bioavailable, so the presence of coal in these benthic sediments confers no adaptive benefit to biota of the marine ecosystem with respect to PAH insults from anthropogenic sources.The source of the background hydrocarbons in benthic sediments of Prince William Sound (PWS), AK, where the 1989 Exxon Valdez oil spill (EVOS) occurred, has been ascribed to oil seeps in coastal areas of the Gulf of Alaska (GOA). We present evidence that coal is a more plausible source, including (i) high concentrations of total PAH (TPAH), between 1670 and 3070 ng/g, in continental shelf sediments adjacent to the coastal region containing extensive coal deposits; (ii) PAH composition patterns of sediments along with predictive models that are consistent with coal but not oil; (iii) low ratios (<0.2) of triaromatic steranes to methylchrysenes found in sediments and coals, contrasting with the high ratios (11 and 13) found in seep oil; and (iv) bioaccumulation of PAH in salmon collected within 100 m of the Katalla oil seeps but not in filter-feeding mussels collected near oilfield drainages 9 km from the seeps, indicating negligible transport of bioavailable PAH from Katalla seeps to the GOA. In contrast with oil, PAH in coal are not bioavailable, so the presence of coal in these benthic sediments confers no adaptive benefit to biota of the marine ecosystem with respect to PAH insults from anthropogenic sources.

Environmental Science & Technology↗
USGS1998

Gas hydrate formation in the deep sea: In situ experiments with controlled release of methane, natural gas, and carbon dioxide

We have utilized a remotely operated vehicle (ROV) to initiate a program of research into gas hydrate formation in the deep sea by controlled release of hydrocarbon gases and liquid CO 2 into natural sea water and marine sediments. Our objectives were to investigate the formation rates and growth patterns of gas hydrates in natural systems and to assess the geochemical stability of the reaction products over time. The novel experimental procedures used the carrying capacity, imaging capability, and control mechanisms of the ROV to transport gas cylinders to depth and to open valves selectively under desired P − T conditions to release the gas either into contained natural sea water or into sediments. In experiments in Monterey Bay, California, at 910 m depth and 3.9 °C water temperature we find hydrate formation to be nearly instantaneous for a variety of gases. In sediments the pattern of hydrate formation is dependent on the pore size, with flooding of the pore spaces in a coarse sand yielding a hydrate cemented mass, and gas channeling in a fine-grained mud creating a veined hydrate structure. In experiments with liquid CO 2 the released globules appeared to form a hydrate skin as they slowly rose in the apparatus. An initial attempt to leave the experimental material on the sea floor for an extended period was partially successful; we observed an apparent complete dissolution of the liquid CO 2 mass, and an apparent consolidation of the CH 4 hydrate, over a period of about 85 days.

Energy and Fuels↗
USGS1998

Carbon isotopic comparisons of oil products used in the developmental history of Alaska

Studies of the fate of oil released into Prince William Sound, AK, as a result of the 1989 Exxon Valdez oil spill, have led to an unexpected discovery. In addition to oil-like residues attributed to the spill, the ubiquitous presence of flattened tar balls, the carbon isotopic compositions of which fall within a surprisingly narrow range [??13C(PDB) = -23.7 ?? 0.3??? (n = 65)], were observed on the shorelines of the northern and western parts of the sound. These compositions are similar to those of some oil products [-23.7 ?? 0.7??? (n = 35)] that were shipped from California and used in Alaska for fuel, lubrication, construction, and paving before ~ 1970. These products include fuel oil, asphalt, and lubricants [-23.8 ?? 0.5??? (n = 11)], caulking, sealants, and roofing tar [-23.7 ?? 0.7??? (n = 16)], and road pavements and airport runways [-23.5 ?? 0.9??? (n = 8)]. Fuel oil and asphalt [-23.5 ?? 0.1??? (n = 3)], stored at the old Valdez town site and spilled during the 1964 Alaskan earthquake, appear to be the source of most of the beached tar balls. Oil products with lighter carbon isotopic compositions, between -25 and -30??? (n = 18), appear to have been used more recently in Alaska, that is, after ~ 1970. The source of some of the products used for modern pavement and runways [-29.3 ?? 0.2??? (n = 6)] is likely Alaskan North Slope crude oil, an example of which was spilled in the 1989 oil spill [-29.2??? (n = 1)].

Chemical Geology↗
USGS1998

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↗
USGS1998

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↗
USGS1997

Chemical and isotopic evidence of gas-influenced flow at a transform plate boundary: Monterey Bay, California

Chemical and isotopic compositions of pore fluids document upward flow through communities of vesicomyid clams in Monterey Bay, California. Within the clam communities, the sulfate reduction zone is only 10 cm thick, and Ca and Mg concentrations decrease to values as low as 2.2 m M and 34.5 m M , respectively, at depths less than 30 cm below the sediment-water interface. Less than 5 m outside the communities, the base of the sulfate reduction zone is deeper than the greatest penetration of the cores (∼30 cm), and Ca and Mg exhibit only minor changes from seawater values. The sediment exhibits no significant variation in grain size, mineralogy, organic carbon, nitrogen, or carbonate content throughout the region. The composition of pore fluid within clam communities results from upward flow of altered fluid rather than different diagenetic reactions within and outside the communities. Isotopically light dissolved inorganic carbon (DIC), with δ 13 C values ranging from −3.2 to −54.1‰, could reflect carbon sources from either oxidized thermogenic methane and/or a mixture of oxidized microbial methane and solid organic carbon. The C 1 /(C 2 +C 3 ) ratios (ranging from 34 to 1142) and the hydrogen and carbon isotopic compositions of methane (δD values of −109 to −156‰; δ 13 C values of −30.6 to −86.6‰) suggest that methane is primarily microbial but that a minor component could be thermally generated. Any thermogenic methane would have migrated from great depths, possibly >2 km. The presence of methane is likely to contribute to fluid flow by reducing the density of the fluids. Past fluid migration and venting are reflected by widespread carbonate mineralization at the sediment-water interface. This mineralization and the geographic distribution and proportions of microbial and thermogenic methane suggest that vent sites migrate when permeability is reduced during carbonate cementation. These results demonstrate that along with convergent and divergent plate boundaries, transform plate boundaries are characterized by fluid flow and that the flow may be widespread, occurring at sites away from fault zones.

Journal of Geophysical Research B: Solid Earth↗
USGS1997

Carbon isotope systematics of individual hydrocarbons in hydrothermal petroleum from Escanaba Trough, Northeastern Pacific Ocean

We submitted individual aliphatic and polycyclic aromatic hydrocarbons in samples of hydrothermal petroleum from Escanaba trough to compound specific isotope analysis to trace their origins. The carbon isotope compositions of the alkanes and polycyclic aromatic hydrocarbons (means -27.5 and -24.7%, respectively) reflect a primarily terrestrial organic matter source.We submitted individual aliphatic and polycyclic aromatic hydrocarbons in samples of hydrothermal petroleum from Escanaba Trough to compound specific isotope analysis to trace their origins. The carbon isotope compositions of the alkanes and polycyclic aromatic hydrocarbons (means -27.5 and -24.7 per mill, respectively) reflect a primarily terrestrial organic matter source.

Organic Geochemistry↗
USGS1997

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↗
USGS1996

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↗
USGS1993

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↗
USGS1993

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↗
USGS1993

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↗