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Keith A. Kvenvolden

Publications and source records attributed to Keith A. Kvenvolden.

At least 37 records · Page 2Linked to original sources

Subsurface and petroleum geology of the southwestern Santa Clara Valley ("Silicon Valley"), California

Gravity anomalies, historical records of exploratory oil wells and oil seeps, new organic-geochemical results, and new stratigraphic and structural data indicate the presence of a concealed, oil-bearing sedimentary basin beneath a highly urbanized part of the Santa Clara Valley, Calif. A conspicuous isostatic-gravity low that extends about 35 km from Palo Alto southeastward to near Los Gatos reflects an asymmetric, northwest-trending sedimentary basin comprising low-density strata, principally of Miocene age, that rest on higher-density rocks of Mesozoic and Paleogene(?) age. Both gravity and well data show that the low-density rocks thin gradually to the northeast over a distance of about 10 km. The thickest (approx 4 km thick) accumulation of low-density material occurs along the basin's steep southwestern margin, which may be controlled by buried, northeast-dipping normal faults that were active during the Miocene. Movement along these hypothetical normal faults may been contemporaneous (approx 17–14 Ma) with sedimentation and local dacitic and basaltic volcanism, possibly in response to crustal extension related to passage of the northwestward-migrating Mendocino triple junction. During the Pliocene and Quaternary, the normal faults and Miocene strata were overridden by Mesozoic rocks, including the Franciscan Complex, along northeastward-vergent reverse and thrust faults of the Berrocal, Shannon, and Monte Vista Fault zones. Movement along these fault zones was accompanied by folding and tilting of strata as young as Quaternary and by uplift of the modern Santa Cruz Mountains; the fault zones remain seismically active. We attribute the Pliocene and Quaternary reverse and thrust faulting, folding, and uplift to compression caused by local San Andreas Fault tectonics and regional transpression along the Pacific-North American Plate boundary. Near the southwestern margin of the Santa Clara Valley, as many as 20 exploratory oil wells were drilled between 1891 and 1929 to total depths as great as 840 m. At least one pump unit is still standing. Although no lithologic or paleontologic samples are available from the wells, driller's logs indicate the presence of thick intervals of brown shale and sandstone resembling nearby outcrops of the Miocene Monterey Formation. Small amounts of oil and gas were observed in several wells, but commercial production was never established. Oil from the Peck well in Los Gatos is highly biodegraded, contains biomarkers commonly found in oils derived from the Monterey Formation, and has a stable-C-isotopic (d13C) composition of –23.32 permil, indicating derivation from a Miocene Monterey Formation source rock. Preliminary calculations suggest that about 1 billion barrels of oil may have been generated from source rocks within the Monterey Formation in the deepest part of the subsurface sedimentary basin between Los Gatos and Cupertino. Most of this oil was probably lost to biodegradation, oxidation, and leakage to the surface, but some oil may have accumulated in as-yet-undiscovered structural and stratigraphic traps along the complex structural boundary between the Santa Clara Valley and the Santa Cruz Mountains. Although some of these undiscovered accumulations of oil may be of commercial size, future petroleum exploration is unlikely because most of the area is currently devoted to residential, recreational, commercial, and industrial uses.

California

Hydrologic setting and geochemical characterization of free-phase hydrocarbons in the alluvial aquifer at Mandan, North Dakota, November 2000

Free-phase hydrocarbons are present in the alluvial aquifer at Mandan, North Dakota. A large contaminant body of the hydrocarbons [light nonaqueous phase liquid (LNAPL)] floats on the water table about 20 feet below land surface. The main LNAPL body is about 6 feet thick, and the areal extent is about 657,000 square feet. A study was conducted to describe the hydrologic setting and characterize the geochemical composition of the free-phase hydrocarbons in the alluvial aquifer. Most of the study area is underlain by alluvium of the Heart River Valley that ranges in thickness from about 25 to 109 feet. The alluvium can be divided into three stratigraphic units silty clay, silty sand, and sand and is underlain by shales and sandstones. Monitoring wells were installed prior to this study, to an average depth of about 29 feet. Regional ground-water flow in the Heart River aquifer generally may be from west-northwest to eastsoutheast and is influenced by hydraulic connections to the river. Hydraulic connections also are probable between the aquifer and the Missouri River. Ground-water flow across the north boundary of the aquifer is minimal because of adjacent shales and sandstones of relatively low permeability. Recharge occurs from infiltration of precipitation and is spatially variable depending on the thickness of overlying clays and silts. Although the general water-table gradient may be from west-northwest to east-southeast, the flow directions can vary depending on the river stage and recharge events. Any movement of the LNAPL is influenced by the gradients created by changes in water-level altitudes. LNAPL samples were collected from monitoring wells using dedicated bailers. The samples were transferred to glass containers, stored in the dark, and refrigerated before shipment for analysis by a variety of analytical techniques. For comparison purposes, reference-fuel samples provided by the refinery in Mandan also were analyzed. These reference-fuel samples included a current diesel fuel, a closely related but slightly broader refinery-cut fuel, a crude-oil composite, unleaded regular gasoline, and additives. Four principal analytical techniques were used for geochemical characterization: Purge-and-trap gas chromatography/mass spectrometry (volatile components); capillary gas chromatography/mass spectrometry (semivolatile components); isotope ratio mass spectrometry (carbon isotopes; whole oils); and liquid chromatography/mass spectrometry with electrospray ionization (additives and other organic components). Volatile analytes included solvents, disinfection byproducts, halogenated hydrocarbons, and alkylbenzenes, including benzene, toluene, ethylbenzene, and meta-, para-, and orf/zo-xylenes. Semivolatile analytes included rt-alkanes, isoprenoid alkanes, cycloalkanes, and polycyclic aromatic hydrocarbons and related compounds (naphthalenes, phenanthrenes, and dibenzothiophenes and their alkylated derivatives). Of the additives, only the diesel-fuel additive with the red dye marker was amenable to electrospray ionization. Results indicate the LNAPL consists of closely correlatable diesel fuel at various stages of degradation. All LNAPL samples contained the red dye marker for diesel fuel. None of the samples contained chlorinated solvents associated with industries such as drycleaning or automotive maintenance. Solvents such as acetone, dimethyl ether, and methylene chloride and the gasoline additives methyl-t-butyl ether (MTBE), ethyl-t-butyl ether (ETBE), and t-amyl-methyl ether (TAME) were not found. With one possible exception, no evidence of a different diesel or other hydrocarbon fuel contribution was identified. At one site near the north edge of the main LNAPL body, evidence exists for traces of possible gasoline components in addition to the diesel fuel. The geochemical analysis of the LNAPL and correlations with other fuel products and additives strongly suggest episodic releases of a single, local-source, diesel fuel into the aquifer over an extended period of time.

North Dakota

Comparison of offshore and onshore gas occurrences, Eel River basin, northern California

The Eel River basin of northern California is a upper Cenozoic depocenter containing more than 3,000 meters of sedimentary rock located near the Mendocino triple junction. Active tectonism has resulted in folding, faulting and rapid sedimentation. Both thermogenic and microbial hydrocarbons are known to be present in the sediments. In August 1997, we sampled two submarine gas seeps, one at a water depth of 520 m that supports a chemosynthetic-based ecosystem very near an area of previously recovered gas hydrate. Another vent site was sampled in sand covered with white bacterial mats at a water depth 41 m. We compared the hydrocarbon gas composition and methane isotopic composition of these seeps with land-based gas occurrences that include: 1) a gas seep and 2) gas from a 2360 m-deep gas well.

California

Reclamation of Bay wetlands and disposal of dredge spoils: meeting two goals simultaneously

San Francisco Bay is one of the world's largest urbanized estuarine systems with a watershed that drains about 40 percent of the State of California. Its freshwater and saltwater marshes comprise approximately 125 square kilometers (48 square miles), compared to 2,200 square kilometers (850 square miles) before California began rapid development in 1850. This staggering reduction in tidal wetlands of approximately 95 percent has resulted in significant loss . of habitat for many species of fish and wildlife. The need for wetlands is well documented- healthy and adequate wetlands are critical to the proper functioning of an estuarine ecosystem like San Francisco Bay.

California

Organic geochemistry applied to environmental assessments of Prince William Sound, Alaska, after the Exxon Valdez oil spill—a review

Organic geochemistry played a major role in the environmental assessments conducted following the Exxon Valdez oil spill, which occurred on March 24, 1989, and released about 258,000 bbls (41 million liters) of Alaska North Slope crude oil into Prince William Sound. Geochemical analyses of more than 15,000 sediment, tar, and biological samples and about 5000 water samples provide the largest database yet collected on oil-spill chemistry, and we review the results here. The marine environment of the Sound has a complex background of petrogenic, pyrogenic, and biogenic hydrocarbons from natural and anthropogenic sources. Geochemical evaluation of the fate and effects of the spilled oil required that this oil and its residues be distinguished from the background. A variety of molecular and isotopic techniques were employed to identify various hydrocarbon sources and to distinguish quantitatively among mixed sources in the samples. Although the specific criteria used to distinguish multiple sources in the region affected by the Exxon Valdez spill are not necessarily applicable to all spill situations, the principles that governed their selection are. Distributions of polycyclic aromatic hydrocarbons (PAH) and dibenzothiophenes distinguish Exxon Valdez oil and its weathered residues from background hydrocarbons in benthic sediments. Ratios of C 2 -dibenzothiophene C 2 -phenanthrene "> C 2 -dibenzothiopheneC 2 -phenanthrene and C 3 -dibenzothiophene C 3 -phenanthrene "> C 3 -dibenzothiopheneC 3 -phenanthrene were particularly useful. Carbon isotopes and terpane distributions distinguished Exxon Valdez residues found on shorelines from tars from other sources. Diesel and diesel soot were identified by the absence of alkylated chrysenes and a narrow distribution of n -alkanes, whereas pyrogenic products were distinguished by the dominance of 4- to 6-ring PAH over 2- to 3-ring PAH and by the dominance of non-alkylated over alkylated homologues of each PAH series. The presence of 18α(H)-oleanane in benthic sediments, coupled with its absence in Exxon Valdez oil and its residues, confirm another petrogenic source. Results of geochemical studies suggest that the petrogenic component in the background of benthic sediments is derived from oil seeps in the eastern Gulf of Alaska. In 1990 and 1991, Exxon Valdez residues, generally forming a small increment to the pre-spill background, were found to be only sporadically distributed in some shallow, near shore sediments adjacent to shorelines that had been heavily oiled in 1989. In 1994, occurrences of Exxon Valdez tars on shoreline surfaces were rare, although residues could be found buried in shoreline sediments at some isolated locations along the spill path where they were protected from wave action. Spilled oil residues collected 16 months after the spill were degraded, on average, by nearly 50%. Shoreline residues from sources other than the spill were also identified and are widespread throughout the Sound. These residues include (1) geochemically distinct tars and oils imported from California oil fields to Alaska for fuel and construction purposes prior to the discovery of the Cook Inlet and North Slope oil fields, (2) diesel and diesel soot, and (3) more highly refined products. Of the more than 2700 chemical analyses of biological samples of higher life forms (fish, birds, and mammals) about 150 (6%) indicate recognizable residues of Exxon Valdez oil, which were identified by their distribution of polycyclic aromatic hydrocarbons (PAH). Most of these samples (138) were collected in 1989 and most were associated with external surfaces or the gastrointestinal tract. Rarely do internal tissues or fluids contain recognizable fingerprints of spilled oil. This observation includes samples from marine mammals that were visibly oiled externally. Other hydrocarbon sources, including diesel and a non-petroleum artifact that occurs when concentrations of individual PAH are at or near their method detection limit, are also identified in biological samples.

Alaska

A review of the geochemistry of methane in natural gas hydrate

The largest accumulations on Earth of natural gas are in the form of gas hydrate, found mainly offshore in outer continental margin sediment and, to a lesser extent, in polar regions commonly associated with permafrost. Measurements of hydrocarbon gas compositions and of carbon-isotopic compositions of methane from natural gas hydrate samples, collected in subaquatic settings from around the world, suggest that methane guest molecules in the water clathrate structures are mainly derived by the microbial reduction of CO 2 from sedimentary organic matter. Typically, these hydrocarbon gases are composed of > 99% methane, with carbon-isotopic compositions (δ 13 C PDB ) ranging from − 57 to − 73‰. In only two regions, the Gulf of Mexico and the Caspian Sea, has mainly thermogenic methane been found in gas hydrate. There, hydrocarbon gases have methane contents ranging from 21 to 97%, with δ 13 C values ranging from − 29 to − 57‰. At a few locations, where the gas hydrate contains a mixture of microbial and thermal methane, microbial methane is always dominant. Continental gas hydrate, identified in Alaska and Russia, also has hydrocarbon gases composed of > 99% methane, with carbon-isotopic compositions ranging from − 41 to − 49‰. These gas hydrate deposits also contain a mixture of microbial and thermal methane, with thermal methane likely to be dominant.

Organic Geochemistry

Maps showing isotopic composition of methane in seawater of the Alaskan Beaufort Sea, 1994

We are engaged in a five-year study to test the hypothesis that methane from decomposing gas hydrates may contribute methane to the atmosphere. The release of methane, a "greenhouse" gas, can enhance global warming and be a factor in global climate change. As part of the study we have measured the methane concentration in the water column of the Beaufort Sea shelf out to water depths of 90 meters from 1992-1995. In 1994 the carbon isotopic composition of methane in seawater of the Beaufort Sea shelf from Cape Halkett to Mikkelsen Bay (total water depths from 3 to 56 m) was measured by gas chromatography-isotope-ratio mass spectrometry in an effort to define the source of methane. Concentrations of methane in water samples used for isotopic analysis ranged from 5.4 to 275 nM.

Alaska

Methane in coastal sea water, sea ice, and bottom sediments, Beaufort Sea, Alaska

This report summarizes data acquired from 1990 to 1994 for the gas-hydrate portion of the USGS project 'Permafrost and gas hydrate as possible sources of methane' of the USGS Global Change and Climate History program. The objective of this project has been to test the hypothesis that gas hydrate deposits of the Beaufort Sea continental shelf are destabilized by the ~10?C temperature increase that has resulted from the Holocene transgression of the Arctic Ocean. To test this idea we have selected an area off the north coast of Alaska centered on Harrison Bay. We have measured the concentration of methane in surficial sediments, in the water column when ice is present and absent, and in seasonal sea ice. Our results show that more methane is present in the water when ice is present than when ice is absent, and that methane is also present within the ice itself, often at higher concentrations than in the water. Thus the Beaufort Sea shelf of Alaska is a seasonal source of methane. The primary source of this methane has not yet been defined, but gas hydrate is a reasonable candidate.

Open-File Report

Laboratory simulation of hydrothermal petroleum formation from sediment in Escanaba Trough, offshore from northern California

Petroleum associated with sulfide-rich sediment is present in Escanaba Trough at the southern end of the Gorda Ridge spreading axis offshore from northern California within the Exclusive Economic Zone (EEZ) of the U.S. This location and occurrence are important for evaluation of the mineral and energy resource potential of the seafloor under U.S. jurisdiction. In Escanaba Trough, petroleum is believed to be formed by hydrothermal processes acting on mainly terrigenous organic material in Quaternary, river-derived sediment. To attempt to simulate these processes in the laboratory, portions of a Pleistocene gray-green mud, obtained from ∼ 1.5 m below the seafloor at a water depth of ∼ 3250 m in Escanaba Trough, were heated in the presence of water in four hydrous-pyrolysis experiments conducted at temperatures ranging from 250 to 350°C and at a pressure of 350 bar for 1.0–4.5 days. Distributions of n -alkanes, isoprenoid hydrocarbons, triterpanes, and steranes in the heated samples were compared with those in a sample of hydrothermal petroleum from the same area. Mud samples heated for less than 4.5 days at less than 350°C show changes in some, but not all, molecular marker ratios of organic compounds that are consistent with those expected during hydrothermal petroleum formation. Our results suggest that the organic matter in this type of sediment serves as one possible source for some of the compounds found in the hydrothermal petroleum.

California

Geochemical changes in crude oil spilled from the Exxon Valdez supertanker into Prince William Sound, Alaska

North Slope crude oil spilled from the T/V Exxon Valdez in March 1989 and contaminated about 500 km of Prince William Sound shoreline. Aliphatic and aromatic hydrocarbons in oil samples collected in August 1990 and June 1992 from beaches on six islands impacted by the spill have been compared with the hydrocarbons from North Slope crude oil taken from the stricken tanker. Degradation processes have changed the physical appearance of this residual spilled oil; the beached oil as collected ranged from a light brown color, to a heavy black viscous oil, to a black, powder-like residue. In these physically different samples, terpane, sterane, and aromatic sterane distributions, as well as carbon isotope values, are similar and correlate with the original Exxon Valdez oil. On the other hand, n -alkanes, isoprenoids, and many of the polycyclic aromatic hydrocarbons which are present in the original crude oil are dramatically altered in the oil samples collected from the beaches.

Alaska

Comparison of 14C ages of hydrothermal petroleums

In order to set limits on the time frame of formation of hydrothermal petroleum, we have obtained 14 C ages on samples from three diverse regions; Gulf of California (Guaymas Basin), Northeast Pacific Ocean (Escanaba Trough and Middle Valley), and the East African Rift (Tanganyika Trough). The results date the source of carbon and therefore provide maximum ages for the formation and emplacement of the hydrothermal petroleums. The youngest petroleum occurs iin the Souther Trough of Guaymas Basin (3200–6600 yr, mean 4692 yr); in the Northern Trough the petroleum is slightly older (7400 yr). Significantly older hydrothermal petroleum occurs in Escanaba Trough (17,000 yr) and Middle Valley (29,000 yr). A continental example from the East African Rift has an age of 25,000 yr, comparable to the ages observed in the oceanic samples from the Northeast Pacific Ocean. These ages affirm that hydrothermal petroleum formation is a very rapid process and took place some time between the latest Pleistocene and the present in these active hydrothermal systems.

Organic Geochemistry

A survey of molecular marker compounds in sediments of San Francisco Bay, California

An areal survey of surficial sediments in San Francisco Bay has been conducted to evaluate the presence of extractable organic compounds. Molecular marker compounds studied include hydrocarbons (PAH's), chlorinated pesticides, and other organic compounds that provide information on sources of organic input into the Bay. Fairly uniform source profiles are seen throughout the Bay. Biomarker profiles contain mature constituents indicating anthropogenic influences and extensive sediment reworking. The dominant input signatures in San Francisco Bay sediment are those of anthropogenic PAH's from combustion and other sources, and long chain n-alkanes and n-aldehydes from terrigenous vascular plants. A comparison of the sums of the combustion PAH's and the terrigenous n-alkanes shows that an anthropogenic influence is dominant in the most urban parts of the Bay close to shore, and in mid-Bay channel areas, and a terrigenous signature is dominant nearshore in San Pablo Bay and at the southernmost station in South Bay.

California