Sulfur isotopic composition of cenozoic seawater sulfate

A continuous seawater sulfate sulfur isotope curve for the Cenozoic with a resolution of approximately 1 million years was generated using marine barite. The sulfur isotopic composition decreased from 19 to 17 per mil between 65 and 55 million years ago, increased abruptly from 17 to 22 per mil between 55 and 45 million years ago, remained nearly constant from 35 to approximately 2 million years ago, and has decreased by 0.8 per mil during the past 2 million years. A comparison between seawater sulfate and marine carbonate carbon isotope records reveals no clear systematic coupling between the sulfur and carbon cycles over one to several millions of years, indicating that changes in the burial rate of pyrite sulfur and organic carbon did not singularly control the atmospheric oxygen content over short time intervals in the Cenozoic. This finding has implications for the modeling of controls on atmospheric oxygen concentration.     

Carbon-13--rich diagenetic carbonates in miocene formations of california and Oregon

Carbon unusually rich in C(13)(deltaC(13) = +5.4 to +19.0 per mil relative to the Peedee belemnite carbonate standard of the University of Chicago) is characteristic of certain diagenetic limestones and dolomites in the Miocene Monterey Shale of California and the Nye Mudstone of Oregon. This heavy carbon may have originated through low-temperature equilibration between CO(3)- - and CO(2) in migrating carbonated waters or between CH(4) and CO(2) in natural gas. Light carbon (deltaC(13) = -5.6 to -18.2 per mil) derived through nonequilibrium oxidation of organic matter also occurs in the carbonate of Monterey Shale in some localities, but at most places it is much less common than heavy carbon.     

Methane-derived marine carbonates of pleistocene age

In some calcium carbonate-bearing sandstones from the edge of the continental shelf off the northeast United States, the deltaC(13) range is from -30 and -60 per mil for both aragonite and high-magnesium calcite. The deltaC(13) of co-existing shells of Modiolus sp. is normal (+ 1.7 to -2.7 per mil). The deltaO(18) values of around + 3.5 per mil in all samples suggest deposition at temperatures around 0 degrees C. Quaternary methane oxidized either chemically or microbiologically to carbon dioxide is the probable source of carbon in these carbonates.     

Organogenic elements and compounds in surface samples from the sea of tranquillity

Organogenic elements, mainly carbon, nitrogen, phosphorus, and sulfur are present in the particulate material and in a breccia rock from Tranquillity Base in amounts ranging from 5 to 4200 parts per million. The major compounds of carbon released by heating are carbon monoxide and carbon dioxide; the former predominates. Small amounts of other compounds of carbon have also been observed. Sulfur can be released as hydrogen sulfide by treatment with acid. The carbon isotopic delta(13L)C values are definitely nonterrestrial (+ 13 to + 18.5 per mil).     

Precipitation of sulfide ores and organic matter: sulfate reactions at pine point, Canada

Bitumen is a common associate of carbonate-hosted lead-zinc deposits. On the Pine Point lead-zinc property, Northwest Territories, Canada, there are two forms of bitumen. Unaltered bitumens have atomic hydrogen/carbon ratios of about 1.4, sulfur contents of about 7.8 percent, and sulfur isotope ratios ( section sign(34)S) of approximately +4.6 per mil. Altered bitumens occur in proximity to sulfide ore bodies and white sparry dolomite. Their hydrogen/carbon ratios are about 1.02, the sulfur contents average 22 percent, and the section sign(34)S values are about +12.4 per mil. These data indicate that some bitumen has participated in the thermochemical reduction of sulfate to produce hydrogen sulfide required to precipitate the ores. Mass balance considerations show that the amount and degree of alteration of bitumen is more than adequate to account for the reduced sulfur species (lead, zinc, and iron sulfides) deposited at Pine Point. These reactions may provide an important means of generating the large volumes of sulfide necessary to precipitate ore bodies in carbonate rocks.     

Water, hydrogen, deuterium, carbon, carbon-13, and oxygen-18 content of selected lunar material

The water content of the breccia is 150 to 455 ppm, with a deltaD from-580 to -870 per mil. Hydrogen gas content is 40 to 53 ppm with a deltaD of -830 to -970 per mil. The CO(2) is 290 to 418 ppm with delta (13)C = + 2.3 to + 5.1 per mil and delta(18)O = 14.2 to 19.1 per mil. Non-CO(2) carbon is 22 to 100 ppm, delta(13)C = -6.4 to -23.2 per mil. Lunar dust is 810 ppm H(2)O (D = 80 ppm) and 188 ppm total carbon(delta(13)C = -17.6 per mil). The (18)O analyses of whole rocks range from 5.8 to 6.2 per mil. The temperature of crystallization of type B rocks is 1100 degrees to 1300 degrees C, based on the oxygen isotope fractionation between coexisting plagioclase and ilmenite.     

Water and carbon in rusty lunar rock 66095

Lunar rock 66095 contains a hydrated iron oxide and has an unusual amount of water for a lunar rock (140 to 750 parts per million), 90 percent of which is released below 690 degrees C. The deltaof water released at these low temperatures varies from -75 to -140 per mil relative to standard mean ocean water (SMOW). The small amount of water released between 690 degrees and 1300 degrees C has a delta of about -175 +/-25 per mil SMOW. These delta values are not unusual for terrestrial water. The delta(18)O of water extracted from 110 degrees to 400 degrees C has a value of +5+/- I per mil SMOW, similar to the value for lunar silicates from rock 66095 and different from the value of -4 to -22 per mil found for samples of terrestrial rust including samples of rusted meteoritic iron. The amount of carbon varies from 11 to 59 parts per million with a delta(13)C from -20 to -30 per mil relative to Pee Dee belemnite. Only very small amounts of reduced species (such as hydrogen, carbon monoxide, and methane) were found, in contrast to the analyses of other lunar rocks. Although it is possible that most of the water in the iron oxide (goethite) may be terrestrial in origin or may have exchanged with terrestrial water during sample return and handling, evidence presented herein suggests that this did not happen and that some lunar water may have a deltaD that is indistinguishable from that of terrestrial water.     

A new type of meteoritic diamond in the enstatite chondrite abee

Diamonds with delta(13)C values of -2 per mil and less than 50 parts per million (by mass) nitrogen have been isolated from the Abee enstatite chondrite by the same procedure used for concentrating Cdelta, the putative interstellar diamond found ubiquitously in primitive meteorites and characterized by delta(13)C values of -32 to -38 per mil, nitrogen concentrations of 2,000 to 12,500 parts per million, and delta(15)N values of -340 per mil. Because the Abee diamonds have typical solar system isotopic compositions for carbon, nitrogen, and xenon, they are presumably nebular in origin rather than presolar. Their discovery in an unshocked meteorite eliminates the possibility of origins normally invoked to account for diamonds in ureilites and iron meteorites and suggests a low-pressure synthesis. The diamond crystals are approximately 100 nanometers in size, are of an unusual lath shape, and represent approximately 100 parts per million of Abee by mass.     

Carbon isotopic studies of organic matter in precambrian rocks

Reduced carbon in early Precambrian cherts of the Fig Tree and upper and middle Onverwacht groups of South Africa is isotopically similar (the average value of delta(13)C(PDB) is -28.7 per mil) to photosynthetically produced organic matter of younger geological age. Reduced carbon in lower Onverwacht cherts (Theespruit formation) is anomalously heavy (the average value of delta(13)C(PDB) is -16.5 per mil). This discontinuity may reflect a major event in biological evolution.     

Carbon-13/carbon-12 isotope fractionation of organic matter associated with uranium ores induced by alpha irradiation

Analyses of stable carbon isotopes from two sample suites from sandstone uranium (tabular) ores show interesting variations. Organic carbon associated with high-grade uranium ore is heavy (delta(13)C = -16.9 to -19.6 per mil, where delta(13)C = (13)C/(12)C relative to the Pee Dee belemnite standard) relative to the adjacent lower-grade samples (-22.7 to -26.4 per mil). It is suggested that the heavy isotopic values for the are samples are related to a radiation and chemical isotope effect that has occurred mainly because of an alpha-radiation dose of 10(11) rads.     

Carbon, carbides, and methane in an apollo 12 sample

Total carbon in the Apollo 12 sample 12023 fines was 110 micrograms per gram of sample with a carbon isotopic abundance delta(13)C (relative to the Pee Dee belemnite standard) of +12 per mil. Hydrolysis of the fines with deuterium chloride yielded undeuterated methane along with deuterated hydrocarbons, thus confirming the presence of 7 to 21 micrograms of carbon per gram of sample as carbide and about 2 micrograms of carbon per gram of sample as indigenous methane. After vacuum pyrolysis of the fines to 1100 degrees C the following gases were detected in the relative abundance: carbon monoxide carbon dioxide methane. Variations of the delta(13)C value with the pyrolysis temperature indicated the presence of carbon with more than one range of isotopic values. The observed delta(13)C value of +14 per mil for lunar carbide is much higher than that of carbide in meteorites. These results suggest that lunar carbide is either indigenous to the moon or a meteoritic contribution that has been highly fractionated isotopically.     

Stable-carbon isotope ratios as a measure of marine versus terrestrial protein in ancient diets

The stable-carbon isotope ratios for the flesh of marine and terrestrial animals from Canada's Pacific coast differ by 7.9 +/- 0.4 per mil, reflecting the approximately 7 per mil difference between oceanic and atmospheric carbon. This difference is passed on to human consumers. The carbon isotopic values (delta(13)C) for human collagen thus yield direct information on the relative amounts of marine and terrestrial foods in prehistoric diets.     

Deep-sea hydrocarbon seep communities: evidence for energy and nutritional carbon sources

Mussels, clams, and tube worms collected in the vicinity of hydrocarbon seeps on the Louisiana slope contain mostly "dead" carbon, indicating that dietary carbon is largely derived from seeping oil and gas. Enzyme assays, elemental sulfur analysis, and carbon dioxide fixation studies demonstrate that vestimentiferan tube worms and three clam species contain intracellular, autotrophic sulfur bacterial symbionts. Carbon isotopic ratios of 246 individual animal tissues were used to differentiate heterotrophic (8(13)C = -14 to -20 per mil), sulfur-based (8(13)C = -30 to -42 per mil), and methane-based (8(13)C = <-40 per mil) energy sources. Mussels with symbiotic methanotrophic bacteria reflect the carbon isotopic composition of the methane source. Isotopically light nitrogen and sulfur confirm the chemoautotrophic nature of the seep animals. Sulfur-based chemosynthetic animals contain isotopically light sulfur, whereas methane-based symbiotic mussels more closely reflect the heavier oceanic sulfate pool. The nitrogen requirement of some seep animals may be supported by nitrogen-fixing bacteria. Some grazing neogastropods have isotopic values characteristic of chemosynthetic animals, suggesting the transfer of carbon into the background deep-sea fauna.     

Mass-independent oxygen isotope fractionation in atmospheric CO as a result of the reaction CO + OH

Atmospheric carbon monoxide (CO) exhibits mass-independent fractionation in the oxygen isotopes. An 17O excess up to 7.5 per mil was observed in summer at high northern latitudes. The major source of this puzzling fractionation in this important trace gas is its dominant atmospheric removal reaction, CO + OH --> CO2 + H, in which the surviving CO gains excess 17O. The occurrence of mass-independent fractionation in the reaction of CO with OH raises fundamental questions about kinetic processes. At the same time the effect is a useful marker for the degree to which CO in the atmosphere has been reacting with OH.     

Oxygen isotope ratios in trees reflect mean annual temperature and humidity

Values of the oxygen isotope ratios (delta(18)O) in tree-ring cellulose closely reflect the delta(18)O values in atmospheric precipitation and hence mean annual temperature. The change in delta(18)O in cellulose is 0.41 per mil per degree Celsius for selected near-coastal stations. The values of delta(18)O in precipitation and cellulose also change with altitude, as demonstrated for Mount Rainier, Washington. A temperature lapse rate of 5.2 degrees +/- 0.5 degrees C per 1000 meters calculated from cellulose delta(18)O values agrees with the accepted mean annual lapse rate of 5 degrees C per 1000 meters for this region. Cellulose delta(18)O values and delta(18)O values of carbon dioxide equilibrated with leaf water differ by a fixed 16 per mil.     

Carbon-13/carbon-12 ratio is relatively uniform among honeys

The variability of the carbon-13/carbon-12 ratio in honeys was evaluated preliminary to use of the ratio to detect the addition of high-fructose corn syrup to honey. Eighty-four honey samples representing 34 states and including 37 floral types from 17 plant families were analyzed. The mean value of the per mil increment in carbon-13 (delta13C) for all samples is -25.2 per mil, and the coefficient of variation is 3.7 percent. This is the smallest variation yet encountered for a honey constituent or physical property. The range and magnitude of the values suggest that the floral sources are C(3) plants.     

Submarine seep of carbon dioxide in norton sound, alaska

Earlier workers have described a submarine gas seep in Norton Sound having an unusual mixture of petroleum-like, low-molecular-weight hydrocarbons. Actually, only about 0.04 percent of the seeping gas is hydrocarbons and 98 percent is carbon dioxide. The isotopic compositions of carbon dioxide (delta(13)C(PDB) = -2.7 per mil) and methane (delta(13)C(PDB) = -36 per mil, where PDB is the Peedee belemnite standard) indicate that geothermal processes are active here.     

Oxygen consumption in pelagic marine sediments

Measurements in the interstitial waters of pelagic red clay and carbonate ooze sediments in the central equatorial Pacific show that the dissolved oxygen content decreases with depth and levels off at nonzero values. The supply of reactive organic carbon introduced by bioturbation limits oxygen consumption at depth in the sediment. These gradients should produce diffusive fluxes across the sediment-water interface that average about 8.8 x 10(-14) mole per square centimeter per second or 0.08 milliliter per square meter per hour.     

Interstellar carbon in meteorites

The Murchison and Allende chondrites contain up to 5 parts per million carbon that is enriched in carbon-13 by up to + 1100 per mil (the ratio of carbon-12 to carbon-13 is approximately 42, compared to 88 to 93 for terrestrial carbon). This "heavy" carbon is associated with neon-22 and with anomalous krypton and xenon showing the signature of the s-process (neutron capture on a slow time scale). It apparently represents interstellar grains ejected from late-type stars. A second anomalous xenon component ("CCFXe") is associated with a distinctive, light carbon (depleted in carbon-13 by 38 per mil), which, however, falls within the terrestrial range and hence may be of either local or exotic origin.     

A methanotrophic marine molluscan (bivalvia, mytilidae) symbiosis: mussels fueled by gas

An undescribed mussel (family Mytilidae), which lives in the vicinity of hydrocarbon seeps in the Gulf of Mexico, consumes methane (the principal component of natural gas) at a high rate. The methane consumption is limited to the gills of these animals and is apparently due to the abundant intracellular bacteria found there. This demonstrates a methane-based symbiosis between an animal and intracellular bacteria. Methane consumption is dependent on the availability of oxygen and is inhibited by acetylene. The consumption of methane by these mussels is associated with a dramatic increase in oxygen consumption and carbon dioxide production. As the methane consumption of the bivalve can exceed its carbon dioxide production, the symbiosis may be able to entirely satisfy its carbon needs from methane uptake. The very light (delta(13)C = -51 to -57 per mil) stable carbon isotope ratios found in this animal support methane (delta(13)C = -45 per mil at this site) as the primary carbon source for both the mussels and their symbionts.