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K.A. Kvenvolden

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

At least 19 recordsLinked to original sources

Amino acid geochemistry of fossil bones from the Rancho La Brea asphalt deposit, California

Low aspartic acid d:l ratios and modern collagenlike concentration values indicate that amino acids in bones from the Rancho La Brea asphalt deposit, Los Angeles, California are better preserved than amino acids in bones of equivalent age that have not been preserved in asphalt. Amino acids were recovered from 10 Rancho La Brea bone samples which range in age from less than 200 to greater than 36,000 yr. The calibrated rates of aspartic acid racemization range from 2.1 to 5.0 × 10 −6 yr −1 . Although this wide range of rate constants decreases the level of confidence for age estimates, use of the larger rate constant of 5.0 × 10 −6 yr −1 provides minimum age estimates which fit the known stratigraphic and chronologic records of the Rancho La Brea deposits.

California↗

Application of organic geochemistry to coastal tar residues from central California

Tar residues are common on the coastline of the Monterey Bay National Marine Sanctuary. These coastal tar residues have been washed ashore and usually occur on headlands near the high-tide line. In this study, 18 coastal tar residues were collected and analyzed to determine their carbon isotopic compositions and the values of selected biomarker ratios. All of the residues have very heavy ( 13 C-enriched) carbon isotopic compositions spanning a narrow range (δ 13 C = −22.2 to −23.4‰), and 28,30-bisnorhopane is present in all samples. These same geochemical characteristics are found in Monterey Formation oils from which the coastal tar residues were likely derived. These coastal residues could result from natural seeps or from accidental spills. Statistically the coastal tar residues can be organized into three groups, each of which may represent different spill or seep events. Seven samples of potential local representative sources for the tar residues were examined, but none could account for the coastal tars.

California↗

Origins of organic geochemistry

When organic geochemistry actually began as a recognized geoscience is a matter of definition and perspective. Constraints on its beginning are placed by the historical development of its parent disciplines, geology and organic chemistry. These disciplines originated independently and developed in parallel, starting in the latter half of the 18th century and flourishing thereafter into the 21st century. Organic geochemistry began sometime between 1860 and 1983; I argue that 1930 is the best year to mark its origin.

Organic Geochemistry↗

Natural gas hydrate occurrence and issues

Naturally occurring gas hydrate is found in sediment of two regions: (1) continental, including continental shelves, at high latitudes where surface temperatures are very cold, and (2) submarine outer continental margins where pressures are very high and bottom-water temperatures are near 0??C. Continental gas hydrate is found in association with onshore and offshore permafrost. Submarine gas hydrate is found in sediment of continental slopes and rises. The amount of methane present in gas hydrate is thought to be very large, but the estimates that have been made are more speculative than real. Nevertheless, at the present time there has been a convergence of ideas regarding the amount of methane in gas hydrate deposits worldwide at about 2 x 1016 m3 or 7 x 1017 ft3 = 7 x 105 Tcf [Tcf = trillion (1012) ft3]. The potentially large amount of methane in gas hydrate and the shallow depth of gas hydrate deposits are two of the principal factors driving research concerning this substance. Such a large amount of methane, if it could be commercially produced, provides a potential energy resource for the future. Because gas hydrate is metastable, changes of surface pressure and temperature affect its stability. Destabilized gas hydrate beneath the sea floor leads to geologic hazards such as submarine mass movements. Examples of submarine slope failures attributed to gas hydrate are found worldwide. The metastability of gas hydrate may also have an effect on climate. The release of methane, a 'greenhouse' gas, from destabilized gas hydrate may contribute to global warming and be a factor in global climate change.

Conference Paper↗

Organic geochemistry - A retrospective of its first 70 years

Organic geochemistry had its origin in the early part of the 20th century when organic chemists and geologists realized that detailed information on the organic materials in sediments and rocks was scientifically interesting and of practical importance. The generally acknowledged "father" of organic geochemistry is Alfred E. Treibs (1899-1983), who discovered and described, in 1936, porphyrin pigments in shale, coal, and crude oil, and traced the source of these molecules to their biological precursors. Thus, the year 1936 marks the beginning of organic geochemistry. However, formal organization of organic geochemistry dates from 1959 when the Organic Geochemistry Division (OGD) of The Geochemical Society was founded in the United States, followed 22 years later (1981) by the establishment of the European Association of Organic Geochemists (EAOG). Organic geochemistry (1) has its own journal, Organic Geochemistry (beginning in 1979) which, since 1988, is the official journal of the EAOG, (2) convenes two major conferences [International Meeting on Organic Geochemistry (IMOG), since 1962, and Gordon Research Conferences on Organic Geochemistry (GRC), since 1968] in alternate years, and (3) is the subject matter of several textbooks. Organic geochemistry is now a widely recognized geoscience in which organic chemistry has contributed significantly not only to geology (i.e., petroleum geochemistry, molecular stratigraphy) and biology (i.e., biogeochemistry), but also to other disciplines, such as chemical oceanography, environmental science, hydrology, biochemical ecology, archaeology, and cosmochemistry.

Conference Paper↗

Gaia's breath - Global methane exhalations

Methane (CH4) is the most abundant organic compound in the Earth's atmosphere, where it acts as a greenhouse gas and thus has implications for global climate change. The current atmospheric CH4 budget, however, does not take into account geologically-sourced CH4 seepage. Geological sources of CH4 include natural macro- and micro-seeps, mud volcanoes, and other miscellaneous sources such as gas hydrates, magmatic volcanoes, geothermal regions, and mid-ocean ridges. Macro-seeps contribute ???25 Tg (teragrams) CH4/yr to the atmosphere, whereas, micro-seepage contributes perhaps 7 Tg CH4/yr. Mud volcanoes emit ???5 Tg CH4/yr, and miscellaneous sources emit ???8 Tg CH4/yr to the atmosphere. Thus, the total contribution to the atmosphere from geological sources is estimated to be 45 Tg CH4/yr, which is significant to the atmospheric organic carbon cycle and should be included in any global inventory of atmospheric CH4. We argue that the atmospheric CH4 global inventory of the Interplanetary Panel on Climate Change must be adjusted in order to incorporate geologically-sourced CH4 from naturally occurring seepage.

Marine and Petroleum Geology↗

Natural seepage of crude oil into the marine environment

Recent global estimates of crude-oil seepage rates suggest that about 47% of crude oil currently entering the marine environment is from natural seeps, whereas 53% results from leaks and spills during the extraction, transportation, refining, storage, and utilization of petroleum. The amount of natural crude-oil seepage is currently estimated to be 600,000 metric tons per year, with a range of uncertainty of 200,000 to 2,000,000 metric tons per year. Thus, natural oil seeps may be the single most important source of oil that enters the ocean, exceeding each of the various sources of crude oil that enters the ocean through its exploitation by humankind.

Geo-Marine Letters↗

Methane hydrate in the global organic carbon cycle

The global occurrence of methane hydrate in outer continental margins and in polar regions, and the magnitude of the amount of methane sequestered in methane hydrate suggest that methane hydrate is an important component in the global organic carbon cycle. Various versions of this cycle have emphasized the importance of methane hydrate, and in the latest version the role of methane hydrate is considered to be analogous to the workings of an electrical circuit. In this circuit the methane hydrate is a condenser and the consequences of methane hydrate dissociation are depicted as a resistor and inductor, reflecting temperature change and changes in earth surface history. These consequences may have implications for global change including global climate change.

Terra Nova↗

Ubiquitous tar balls with a California-source signature on the shorelines of Prince William Sound, Alaska

Although the shorelines of Prince William Sound still bear traces of the 1989 Exxon Valdez oil spill, most of the flattened tar balls that can be found today on these shorelines are not residues of Exxon Valdez oil. Instead, the carbon-isotopic and hydrocarbonbiomarker signatures of 61 tar ball samples, collected from shorelines throughout the northern and western parts of the sound, are all remarkably similar and have characteristics consistent with those of oil products that originated from the Monterey Formation source rocks of California. The carbonisotopic compositions of the tar balls are all closely grouped (<513Cpdb = -23.7 ± 0.2%o), within the range found in crude oils from those rocks, but are distinct from isotopic compositions of 28 samples of residues from the Exxon ValdezoW spill (<513Cpdb = -29.4 ± 0.1%o). Likewise, values for selected biomarker ratios in the tar balls are all similar but distinct from values of residues from the 1989 oil spill. Carbon-isotopic and biomarker signatures generally relate the tar balls to oil products used in Alaska before ~1970 for construction and pavements. How these tar balls with such similar geochemical characteristics became so widely dispersed throughout the northern and western parts of the sound is not known with certainty, but the great 1964 Alaska earthquake was undoubtedly an important trigger, causing spills from ruptured storage facilities of California-sourced asphalt and fuel oil into Prince William Sound.

Alaska↗

Alkylcyclohexanes in environmental geochemistry

The n-alkylated cyclohexanes (CHs) are a homologous series of hydrocarbon compounds that are commonly present in crude oil and refinery products such as diesel fuel. These compounds exhibit specific distribution patterns for different fuel types, providing useful fingerprints for characterizing petroleum products, especially after degradation of n-alkanes has occurred. However, there are no published data to show how these compounds are altered in the environment after long-term spillage of petroleum products. This paper presents two case studies of oil spills that demonstrate the changing distribution patterns resulting from long-term anaerobic microbial degradation. These spills are the 1979 crude-oil spill in Bemidji, Minnesota, and a chronic diesel-fuel spillage from 1953-1991 at Mandan, North Dakota. The alkyl CHs in both spilled oil products are affected by similar biodegradative processes in which the compounds undergo a consistent pattern of loss from the high molecular weight end of the homolog distribution. Degradation results in a measurable increase in the concentrations of the homologs in the lower molecular weight range, a gradual lowering in carbon number of the homolog maximum, and a gradual decrease of the total homolog range from the high molecular weight end. This pattern is the opposite of low-end loss expected with weathering and aerobic biodegradation. The enhancement of the low molecular mass alkyl CH homologs, if not recognized as a degradative pathway of diesel fuel in an anaerobic environment, can potentially be misinterpreted in fuel-oil fingerprinting as deriving from lower distillation-range fuels or admixture of diesel with other fuels.

Environmental Forensics↗

Hydrocarbons in recent sediment of the Monterey Bay National Marine Sanctuary

A complex mixture of hydrocarbons is present in the recent sediment of the Monterey Bay National Marine Sanctuary. Eighteen samples from the continental shelf between San Francisco and Monterey contain aliphatic and aromatic hydrocarbons showing biological contributions from both marine and terrigenous sources, with the terrigenous indicators more pronounced near Monterey. Of particular interest, however, is a low-level background of petroleum-related compounds, including 28,30-bisnorhopane and 18??+??(H)-oleanane, which are characteristic of many crude oils from the Monterey Formation of California. Thus, the sediments are overprinted by a regional chemical signature which may be derived from eroded Monterey Formation rocks and from onshore and offshore seeps releasing petroleum from Monterey Formation source rocks. ?? 2002 Elsevier Science B.V. All rights reserved.

Marine Geology↗

Hydrocarbon geochemistry of cold seeps in the Monterey Bay National Marine Sanctuary

Samples from four geographically and tectonically discrete cold seeps named Clam Flat, Clamfield, Horseshoe Scarp South, and Tubeworm City, within the Monterey Bay National Marine Sanctuary were analyzed for their hydrocarbon content. The sediment contains gaseous hydrocarbons and CO2, as well as high molecular weight aliphatic and aromatic hydrocarbons with various combinations of thermogenic and biogenic contributions from petroleum, marine, and terrigenous sources. Of particular interest is the cold seep site at Clamfield which is characterized by the presence of thermogenic hydrocarbons including oil that can likely be correlated with oil-saturated strata at Majors Creek near Davenport, CA, USA. At Clam Flat, the evidence for thermogenic hydrocarbons is equivocal. At Horseshoe Scarp South and Tubeworm City, hydrocarbon gases, mainly methane, are likely microbial in origin. These varied sources of hydrocarbon gases highlight the diverse chemical systems that appear at cold seep communities. ?? 2002 Elsevier Science B.V. All rights reserved.

Marine Geology↗

History of the recognition of organic geochemistry in geoscience

The discipline of organic geochemistry is an outgrowth of the application of the principles and methods of organic chemistry to sedimentary geology. Its origin goes back to the last part of the nineteenth century and the first part of the twentieth century concurrent with the evolution of the applied discipline of petroleum geochemistry. In fact, organic geochemistry was strongly influenced by developments in petroleum geochemistry. Now, however, organic geochemistry is considered an umbrella geoscience discipline of which petroleum geochemistry is an important component.

Organic Geochemistry↗

Alkylcyclohexanes in environmental geochemistry

Two case studies of oil spills that demonstrate the changing distribution patterns resulting from long-term anaerobic microbial degradation were presented. These spills were the 1979 crude-oil spill in Bemidji, MN, and a chronic diesel-fuel spillage from 1953-1991 at Mandan, ND. The alkylcyclohexanes in both spilled oil products were affected by similar biodegradative processes in which the compounds underwent a consistent pattern of loss from the high molecular weight end of the homolog distribution. Degradation resulted in a measurable increase in the concentrations of the homologs in the lower molecular weight range, a gradual lowering in carbon number of the homolog maximum, and a gradual decrease of the total homolog range from the high molecular weight end. The Mandan diesel fuel spill showed that the progressive enhancement of the low-molecular-mass n-alkane and n-alkylcyclohexane homologs reflected an absolute increase in their concentrations as the high-molecular-mass homologs were diminishing. These degradation patterns were different from those observed in aerobic or physically weathered systems, where loss of n-alkenes and other aliphatic homologs occurred from the low molecular weight end of the distributions. Spilled diesel and other mid-cut refinery fuels were defined by the range and distribution of the n-alkylcyclohexanes. If the biodegradation has progressed well into or beyond n-alkane loss and to the stage of low-molecular-mass n-alkylcyclohexane enhancement and high-molecular-mass loss, the hydrocarbon pattern could be erroneously attributed to other lower-range middle distillate fuels or admixtures of fuels. This is an abstract presented at the 25th Arctic and Marine OilSpill Program Technical Seminar (Calgary, Alberta, 6/11-13/2002).

Conference Paper↗

Global occurrences of gas hydrate

Natural gas hydrate is found worldwide in sediments of outer continental margins of all oceans and in polar areas with continuous permafrost. There are currently 77 localities identified globally where geophysical, geochemical and/or geological evidence indicates the presence of gas hydrate. Details concerning individual gas-hydrate occurrences are compiled at a new world-wide-web (www) site (http://walrus.wr.usgs.gov/globalhydrate). This site has been created to facilitate global gas-hydrate research by providing information on each of the localities where there is evidence for gas hydrate. Also considered are the implications of gas hydrate as a potential (1) energy resource, (2) factor in global climate change, and (3) geohazard.

Conference Paper↗

Methane and other hydrocarbon gases in sediment from the southeastern North American continental margin

Residual concentrations and distributions of hydrocarbon gases from methane to n-heptane were measured in sediments at seven sites on Ocean Drilling Program (ODP) Leg 164. Three sites were drilled at the Cape Fear Diapir of the Carolina Rise, and one site was drilled on the Blake Ridge Diapir. Methane concentrations at these sites result from microbial generation which is influenced by the amount of pore-water sulfate and possible methane oxidation. Methane hydrate was found at the Blake Ridge Diapir site. The other hydrocarbon gases at these sites are likely the produce of early microbial processes. Three sites were drilled on a transect of holes across the crest of the Blake Ridge. The base of the zone of gas-hydrate occurrence was penetrated at all three sites. Trends in hydrocarbon gas distributions suggest that methane is microbial in origin and that the hydrocarbon gas mixture is affected by diagenesis, outgassing, and, near the surface, by microbial oxidation. Methane hydrate was recovered at two of these three sites, although gas hydrate is likely present at all three sites. The method used here for determining amounts of residual hydrocarbon gases has its limitations and provides poor assessment of gas distributions, particularly in the stratigraphic interval below about ~ 100 mbsf. One advantage of the method, however, is that it yields sufficient quantities of gas for other studies such as isotopic determinations.

Conference Paper↗

Gas hydrate and humans

The potential effects of naturally occurring gas hydrate on humans are not understood with certainty, but enough information has been acquired over the past 30 years to make preliminary assessments possible. Three major issues are gas hydrate as (1) a potential energy resource, (2) a factor in global climate change, and (3) a submarine geohazard. The methane content is estimated to be between 1015 to 1017 m3 at STP and the worldwide distribution in outer continental margins of oceans and in polar regions are significant features of gas hydrate. However, its immediate development as an energy resource is not likely because there are various geological constraints and difficult technological problems that must be solved before economic recovery of methane from hydrate can be achieved. The role of gas hydrate in global climate change is uncertain. For hydrate methane to be an effective greenhouse gas, it must reach the atmosphere. Yet there are many obstacles to the transfer of methane from hydrate to the atmosphere. Rates of gas hydrate dissociation and the integrated rates of release and destruction of the methane in the geo/hydro/atmosphere are not adequately understood. Gas hydrate as a submarine geohazard, however, is of immediate and increasing importance to humans as our industrial society moves to exploit seabed resources at ever-greater depths in the waters of our coastal oceans. Human activities and installations in regions of gas-hydrate occurrence must take into account the presence of gas hydrate and deal with the consequences of its presence.

Conference Paper↗

Potential effects of gas hydrate on human welfare

For almost 30 years, serious interest has been directed toward natural gas hydrate, a crystalline solid composed of water and methane, as a potential (i) energy resource, (ii) factor in global climate change, and (iii) sub-marine geohazard. Although each of these issues can affect human welfare, only (iii) is considered to be of immediate importance. Assessments of gas hydrate as an energy resource have often been overly optimistic, based in part on its very high methane content and on its worldwide occurrence in continental margins. Although these attributes are attractive, geologic settings, reservoir properties, and phase-equilibria considerations diminish the energy resource potential of natural gas hydrate. The possible role of gas hydrate in global climate change has been often overstated. Although methane is a 'greenhouse' gas in the atmosphere, much methane from dissociated gas hydrate may never reach the atmosphere, but rather may be converted to carbon dioxide and sequestered by the hydrosphere/biosphere before reaching the atmosphere. Thus, methane from gas hydrate may have little opportunity to affect global climate change. However, submarine geohazards (such as sediment instabilities and slope failures on local and regional scales, leading to debris flows, slumps, slides, and possible tsunamis) caused by gas-hydrate dissociation are of immediate and increasing importance as humankind moves to exploit seabed resources in ever-deepening waters of coastal oceans. The vulnerability of gas hydrate to temperature and sea level changes enhances the instability of deep-water oceanic sediments, and thus human activities and installations in this setting can be affected.

Conference Paper↗