Anomalous carbon-isotope ratios in nonvolatile organic material.

Organic mats are associated with sulfur deposits in Upper Pleistocene sand ridges of the coastal plain of southern Israel; black, brittle, and non-volatile, they show parallel layering but no other apparent cellular structure. Two independent carbon-14 determinations yielded ages of 27,750+/-500 and 31,370+/-1400 years. Four carbon-13:carbon-12 determinations fell within the range deltaC(13) =-82.5 to -89.3 per mille relative to the PDB standard; these appear to be the lowest values yet reported for naturally occurring high-molecular-weight organic material. The origin of the carbon is probably complex; it must have passed through at least one biologic cycle before final deposition.

Endogenous carbon in carbonaceous meteorites.

Seven carbonaceous chondrites have been analyzed for soluble organic compounds, carbonate, and residual carbon. Carbon-13/carbon-12 isotopic mneasurements on these fractions gave the following values relative to a marine carbonate standard: carbonate, +40 to +70 per mil; residual carbon, -15 to -17 per mil; soluble organic material, -17 to -27 per mil, with one value of -5.5 per mil. These values are interpreted to indicate that carbonate, residual carbon, and part of the extractable organic material are endogenous to these meteorites.

Concentration and isotopic composition of carbon and sulfur in apollo 11 lunar samples.

The concentration of carbon and sulfur in six samples ranged between 20 to 200 and 650 to 2300 parts per million, respectively. Carbon was present in gaseous, volatilizable, and nonvolatile forms, and terrestrial contaminants were recognized. Sulfur appeared to exist only as acid-volatile sulfide. The bulk fines contain a high concentration of carbon and a low concentration of sulfur. They are always enriched in the heavier isotope carbon-13 or sulfur-34. The fine-grained basaltic rocks show the reverse relation; lowest carbon, highest sulfide concentrations, and no apparent enrichment in heavy isotopes. The breccias are of intermediate composition.

Carbonate compensation depth: relation to carbonate solubility in ocean waters.

In situ calcium carbonate saturometry measurements suggest that the intermediate water masses of the central Pacific Ocean are close to saturation with resppect to both calcite and local carbonate sediment. The carbonate compensation depth, located at about 3700 meters in this area, appears to represent a depth above which waters are essentially saturated with respect to calcite and below which waters deviate toward undersaturation with respect to calcite.

Manganese and related elements in the interstitial water of marine sediments.

Analyses for manganese, nickel, iron, cobalt, sodium, and lithium in the interstitial water of cores from the southern California borderland and six deep-sea cores in the area of the East Pacific Rise show great variation in concentration of trace elements. Oxidizing near-shore sediments showed a 50-fold enrichment in manganese in contrast to sulfide-rich reducing sediments, which showed no enrichment. Deep-sea sediments were variable in their concentration of the trace metals. All but one core showed a high enrichment in dissolved manganese, with a maximum of 6.6 parts per million. Two cores showed a 100-fold enrichment in nickel and cobalt. The manganese appears to be in solution either as Mn(2+) or as a complex. The results appear to support manganese nodule formation in deep-sea sediments through a diffusion of manganese from depth to the surface.

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.

Fly ash-derived strontium as an index to monitor deposition from coal-fired power plants.

The combustion of western U.S. coals releases significant amounts of strontium, which is relatively enriched in the fine particles of fly ash. Fly ash-derived strontium is readily absorbed by agronomic and native plant species when incorporated in soil. The strontium-87 to strontium-86 ratios of fly ash and soils were significantly different, but similar ratios were found in fly ash and plants treated with fly ash. A technique for measuring and monitoring deposition from coal-fired power plants is inferred from the enhanced plant uptake of fly ash strontium and the similarity in the isotopic ratios of fly ash and treated plants.

Organic geochemistry of sediments from the continental margin off southern New England, U.S.A.--Part I. Amino acids, carbohydrates and lignin.

Total organic carbon (TOC), lignin, amino acids, sugars and amino sugars were measured in recent sediments for the continental margin off southern New England. The various organic carbon fractions decreased in concentration with increasing distance from shore. The fraction of the TOC that was accounted for by these major components also decreased with increasing distance from shore. The concentration of lignin indicated that only about 3-5% of the organic carbon in the nearshore sediment was of terrestrial origin. The various fractions were highly correlated, which was consistent with a simple linear mixing model of shelf organic matter with material form the slope and rise and indicated a significant transport of sediment from the continental shelf to the continental slope and rise.

Organic geochemistry of sediments from the continental margin off southern New England, U.S.A.--Part II. Lipids.

Organic geochemical measurements of the lipid fraction, comparing saturated and aromatic hydrocarbons, fatty acids, alcohols and sterols, have been carried out on six sediments cores collected from the Atlantic shelf, slope and the rise areas to evaluate the cross-shelf transport of the organic carbon. The concentration of most of the organic compound classes studied is correlated with the total organic carbon, which decreases from the shelf through slope to the rise. Terrigenous carbon is recognizable even in the slope and rise sediments, but terrestrial influx decreases relative to marine generated lipids in the slope and rise organic matter. We estimate that approximately 50% of the shelf organic matter is exported to the slope. Data of sediment trap material collected at 1200 m from 1250 m water depth are discussed and compared with that of surface sediment from 1280 m water depth (slope). Fluxes for specific organic compound classes have been computed. The fluxes are of the same magnitude as for equatorial North Atlantic trap particulates at comparable water depth, studied by other investigations.

APDC-MIBK extraction system for the determination of trace elements in saline waters by atomic-absorption spectrophotometry.

A technique has been developed for the determination of "soluble" cobalt, copper, iron, lead, nickel and zinc in saline waters by simultaneous extraction of their complexes with ammonium pyrollidine dithiocarbamate (APDC) into methyl isobutyl ketone (MIBK) and subsequent analysis by atomic-absorption spectrophotometry. Particulate matter is analysed separately by dissolving millipore filters in an acetone-hydrochloric acid mixture. Various analytical and instrumental parameters have been evaluated. The method is selfcompensating in that it makes allowance for any incomplete extraction of the complexes. The technique has been applied to the determination of these elements in sea-water and saline lakes.

The role of minerals in the thermal alteration of organic matter--III. Generation of bitumen in laboratory experiments.

A series of pyrolysis experiments, utilizing two different immature kerogens (from the Monterey and Green River Formations) mixed with common sedimentary minerals (calcite, illite, or Na-montmorillonite), was conducted to study the impact of the mineral matrix on the bitumen that was generated. Calcite has no significant influence on the thermal evolution of bitumen and also shows virtually no adsorption capacity for any of the pyrolysate. In contrast, montmorillonite and illite, to a lesser extent, alter bitumen during dry pyrolysis. Montmorillonite and illite also display strong adsorption capacities for the polar constituents of bitumen. By this process, hydrocarbons are substantially concentrated within the pyrolysate that is not strongly adsorbed on the clay matrices. The effects of the clay minerals are significantly reduced during hydrous pyrolysis. The strong adsorption capacities of montmorillonite and illite, as well as their thermocatalytic properties, may in part explain why light oils and gases are generated from certain argillaceous source-rock assemblages, whereas heavy immature oils are often derived from carbonate source rocks.

Biological marker distribution in coexisting kerogen, bitumen and asphaltenes in Monterey Formation diatomite, California.

Organic-rich (18.2%) Monterey Formation diatomite from California was studied. The organic matter consist of 94% bitumen and 6% kerogen. Biological markers from the bitumen and from pyrolysates of the coexisting asphaltenes and kerogen were analyzed in order to elucidate the relationship between the various fractions of the organic matter. While 17 alpha(H), 18 alpha(H), 21 alpha(H)-28,30-bisnorhopane was present in the bitumen and in the pryolysate of the asphaltenes, it was not detected in the pyrolysates of the kerogen. A C40-isoprenoid with "head to head" linkage, however, was present in pyrolysates of both kerogen and asphaltenes, but not in the bitumen from the diatomite. The maturation level of the bitumen, based on the extent of isomerization of steranes and hopanes, was that of a mature oil, whereas the pyrolysate from the kerogen showed a considerably lower maturation level. These relationships indicate that the bitumen may not be indigenous to the diatomite and that it is a mature oil that migrated into the rock. We consider the possibility, however, that some of the 28,30-bisnorhopane-rich Monterey Formation oils have not been generated through thermal degradation of kerogen, but have been expelled from the source rock at an early stage of diagenesis.

Long-chain carboxylic acids in pyrolysates of Green River kerogen.

Long-chain fatty acids (C10-C32), as well as C14-C21 isoprenoid acids (except for C18), have been identified in anhydrous and hydrous pyrolyses products of Green River kerogen (200-400 degrees C, 2-1000 hr). These kerogen-released fatty acids are characterized by a strong even/odd predominance (CPI: 4.8-10.2) with a maximum at C16 followed by lesser amounts of C18 and C22 acids. This distribution is different from that of unbound and bound geolipids extracted from Green River shale. The unbound fatty acids show a weak even/odd predominance (CPI: 1.64) with a maximum at C14, and bound fatty acids display an even/odd predominance (CPI: 2.8) with maxima at C18 and C30. These results suggest that fatty acids were incorporated into kerogen during sedimentation and early diagenesis and were protected from microbial and chemical changes over geological periods of time. Total quantities of fatty acids produced during heating of the kerogen ranged from 0.71 to 3.2 mg/g kerogen. Highest concentrations were obtained when kerogen was heated with water for 100 hr at 300 degrees C. Generally, their amounts did not decrease under hydrous conditions with increase in temperature or heating time, suggesting that significant decarboxylation did not occur under the pyrolysis conditions used, although hydrocarbons were extensively generated.

Volatile organic acids generated from kerogen during laboratory heating.

Low molecular weight organic acids were studied in the course of pyrolysis experiments (200-400 degrees C, 2-1,000 h) of kerogen (Green River Formation and Monterey Formation) with and without the presence of water and minerals (montmorillonite, illite and calcite). C1-C10 aliphatic acids and benzoic acid were identified in the pyrolysis products of kerogen. Their distribution is characterized by a dominance of acetic acid followed by formic and propionic acids with an even/odd preference in the range of C4-C10. Total concentrations of these acids amounted to 0.3% of initial kerogen, indicating that kerogen has a good potential for producing organic acids. Geochemical implications of these organic acids are; (1) they are possible intermediates from kerogen to natural gas (CO2, H2, CH4, C2H6, etc.) by decarboxylation, and (2) they may be important and potential contributors to the generation of secondary porosity by dissolving minerals.

Dicarboxylic acids generated by thermal alteration of kerogen and humic acids.

Significant amounts (up to 2% of organic geopolymers) of low molecular weight (LMW) dicarboxylic acids (C2-C10) have been detected during thermal alteration (270 degrees C, 2 h) of kerogens and humic acids isolated from young or ancient lithified sediments. Their distribution is characterized by predominance of oxalic acid followed by succinic, fumaric and methylsuccinic acids. These acids are probably released by the breakdown of macromolecular structures, which have incorporated biogenic organic compounds, including diacids, during early diagenesis in sediments. Because of their reactivity, LMW diacids may play the following geochemically important roles under natural conditions: (1) the diacids dissolve carbonates and clay minerals to increase porosity and permeability, which enhances migration of oils and gas generated from catagenesis of kerogen dispersed in shale, and (2) the diacids may form organo-metal complexes, which are important for mobilization, transport and accumulation of trace metals in sedimentary basins.

Atmospheric H2O2 measurement: comparison of cold trap method with impinger bubbling method.

Collection of atmospheric H2O2 was performed by a cold trap method using dry ice-acetone as the refrigerant. The air was drawn by a pump into a glass gas trap immersed in the dry ice-acetone slush in a dewar flask at a flow rate of 2.5 l min-1 for approximately 2 h. Collection efficiency was > 99% and negligible interferences by O3, SO2 or organic matter with the collected H2O2 in the trap were observed. This method was compared with the air impinger bubbling method which has been previously described (Kok et al., 1978a, b, Envir. Sci. Technol. 12, 1072-1080). The measured total peroxide (H2O2 + organic peroxide) values in a series of aim samples collected by the impinger bubbling method (0.06-3.7 ppb) were always higher than those obtained by the cold trap method (0.02-1.2 ppb). Laboratory experiments suggest that the difference in values between the two methods probably results from the aqueous phase generation of H2O2 and organic peroxide in the impinger solution by a reaction of atmospheric O3 with olefinic and aromatic compounds. If these O3-organic compound reactions which occur in the impinger also occur in aqueous droplets in the atmosphere, the process could be very important for aqueous phase generation of H2O2 in clouds and rainwater.

Role of minerals in the thermal alteration of organic matter--I: generation of gases and condensates under dry condition.

Pyrolysis experiments were carried out on Monterey formation kerogen and bitumen and Green River formation kerogen (Type II and I, respectively), in the presence and absence of montmorillonite, illite and calcite at 200 and 300 degrees C for 2-2000 hours. The pyrolysis products were identified and quantified and the results of the measurements on the gas and condensate range are reported here. A significant catalytic effect was observed for the pyrolysis of kerogen with montmorillonite, whereas small or no effects were observed with illite and calcite, respectively. Catalytic activity was evident by the production of up to five times higher C1-C6 hydrocarbons for kerogen with montmorillonite than for kerogen alone, and by the dominance of branched hydrocarbons in the C4-C6 range (up to 90% of the total amount at any single carbon number). This latter effect in the presence of montmorillonite is attributed to cracking via a carbonium-ion [carbocation] intermediate which forms on the acidic sites of the day. No catalytic effect, however, was observed for generation of methane and C2 hydrocarbons which form by thermal cracking. The catalysis of montmorillonite was significantly greater during pyrolysis of bitumen than for kerogen, which may point to the importance of the early formed bitumen as an intermediate in the production of low molecular weight hydrocarbons. Catalysis by minerals was also observed for the production of carbon dioxide. These results stress the importance of the mineral matrix in determining the type and amount of gases and condensates forming from the associated organic matter under thermal stress. The literature contains examples of gas distribution in the geologic column which can be accounted for by selective mineral catalysis, mainly during early stages of organic matter maturation.

Low-Mr hydrocarbons generated during hydrous and dry pyrolysis of kerogen.

The validity of applying laboratory pyrolysis experiments to simulating the maturation of organic matter in sedimentary basins has been vigorously debated. We report here results from the generation of hydrocarbons of low relative molecular mass (Mr) in both hydrous and dry pyrolysis. A principal difference is that under dry conditions in the presence of montmorillonite, catalysis occurs with respect to generation of low-Mr hydrocarbons but no such effect is evident for hydrous conditions, probably because of a reduction in the clay's acidity. In addition, olefins which were previously reported as not being present in the products of hydrous pyrolyses were found to be produced in the C2-C6 range in comparable amounts under both hydrous and dry pyrolyses at 300 degrees C and may form in the course of kerogen catagenesis in nature but disappear with geologic time due to their instability. These studies have relevance to understanding the interactions between kerogen and minerals in sedimentary rocks and to processes in the formation of natural gas.

The role of minerals in the thermal alteration of organic matter--IV. Generation of n-alkanes, acyclic isoprenoids, and alkenes in laboratory experiments.

A series of pyrolysis experiments, utilizing two different immature oil-prone kerogens ("type I": Green River Formation kerogen; "Type II": Monterey Formation kerogen) mixed with common sedimentary minerals (calcite, illite, or Na-montmorillonite), was conducted to study the effects of minerals on the generation of n-alkanes, acyclic isoprenoids, and alkenes during laboratory-simulated catagenesis of kerogen. The influence of clay minerals on the aliphatic hydrocarbons is critically dependent on the water concentration during laboratory thermal maturation. Under extremely low contents of water (i.e., dry pyrolysis, where only pyrolysate water is present), C12(+) -range n-alkanes and acyclic isoprenoids are mostly destroyed by montmorillonite but undergo only minor alteration with illite. Both clay minerals significantly reduce alkene formation during dry pyrolysis. Under hydrous conditions (mineral/water = 2:1), the effects of the clay minerals are substantially reduced. In addition, the dry pyrolysis experiments show that illite and montmorillonite preferentially retain large amounts of the polar constituents of bitumen, but not n-alkanes or acyclic isoprenoids. Therefore, bitumen fractionation according to polarity differences occurs in the presence of these clay minerals. By this process, n-alkanes and acyclic isoprenoids are concentrated in the bitumen fraction that is not strongly adsorbed on the clay matrices. The extent of these concentrations effects is greatly diminished during hydrous pyrolysis. In contrast, calcite has no significant influence on the thermal evolution of the hydrocarbons. In addition, calcite is incapable of retaining bitumen. Therefore, the fractionation of n-alkanes or acyclic isoprenoids relative to the polar constituents of bitumen is insignificant in the presence of calcite.

Methanogenesis from acetate: a nonmethanogenic bacterium from an anaerobic acetate enrichment.

A methanogenic acetate enrichment was initiated by inoculation of an acetate-mineral salts medium with domestic anaerobic digestor sludge and maintained by weekly transfer for 2 years. The enrichment culture contained a Methanosarcina and several obligately anaerobic nonmethanogenic bacteria. These latter organisms formed varying degrees of association with the Methanosarcina, ranging from the nutritionally fastidious gram-negative rod called the satellite bacterium to the nutritionally nonfastidious Eubacterium limosum. The satellite bacterium had growth requirements for amino acids, a peptide, a purine base, vitamin B12, and other B vitamins. Glucose, mannitol, starch, pyruvate, cysteine, lysine, leucine, isoleucine, arginine, and asparagine stimulated growth and hydrogen production. Acetate was neither incorporated nor metabolized by the satellite organism. Since acetate was the sole organic carbon source in the enrichment culture, organism(s) which metabolize acetate (such as the Methanosarcina) must produce substrates and growth factors for associated organisms which do not metabolize acetate.