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At least 163 records · Page 9Linked to original sources

Microbial methane in the shallow Paleozoic sediments and glacial deposits of Illinois, U.S.A.

Methane formed by the microbial decomposition of buried organic matter is virtually ubiquitous in the groundwaters of Illinois. Chemical and carbon isotopic compositions are reported for gas samples collected from over 200 private and municipal water wells and from 39 small gas wells completed in glacial deposits (drift-gas wells). Carbon and hydrogen isotopic data for methane, carbon dioxide and water show that these gases were formed by the carbon dioxide reduction pathway, the same mechanism which has been previously shown to be responsible for microbial methane formation in the marine environment. The isotopic composition of methane in these samples can be closely correlated with the chemical composition of the gas and with water chemistry. The data are interpreted as indicating that isotopically very light methane is found in waters where the residence time of groundwater in the methanogenesis zone was very short relative to the methane production rate. ?? 1988.

Chemical Geology↗

Methane hydrate - A major reservoir of carbon in the shallow geosphere?

Methane hydrates are solids composed of rigid cages of water molecules that enclose methane. Sediment containing methane hydrates is found within specific pressure-temperature conditions that occur in regions of permafrost and beneath the sea in outer continental margins. Because methane hydrates are globally widespread and concentrate methane within the gas-hydrate structure, the potential amount of methane present in the shallow geosphere at subsurface depths of < ???2000 m is very large. However, estimates of the amount are speculative and range over about three orders of magnitude, from 2 ?? 103 to 4 ?? 106 Gt (gigatons = 1015 g) of carbon, depending on the assumptions made. The estimate I favor is ??? 1 ?? 104 Gt of carbon. The estimated amount of organic carbon in the methane-hydrate reservoir greatly exceeds that in many other reservoirs of the global carbon cycle - for example, the atmosphere (3.6 Gt); terrestrial biota (830 Gt); terrestrial soil, detritus and peat (1960 Gt); marine biota (3 Gt); and marine dissolved materials (980 Gt). In fact, the amount of carbon may exceed that in all fossil fuel deposits (5 ?? 103 Gt). Because methane hydrates contain so much methane and occur in the shallow geosphere, they are of interest as a potential resource of natural gas and as a possible source of atmospheric methane released by global warming. As a potential resource, methane hydrates pose both engineering and production problems. As a contributor to a changing global climate, destabilized methane hydrates, particularly those in shallow, nearshore regions of the Arctic Ocean, may have some effect, but this effect will probably be minimal, at least during the next 100 years. ?? 1988.

Chemical Geology↗

Character, origin and occurrence of natural gases in the Anadarko basin, southwestern Kansas, western Oklahoma and Texas Panhandle, U.S.A.

Natural gas production in the Anadarko basin comes from three geographically separated areas that can be differentiated by age of reservoir and by inferred nature of organic, thermal origin of the gases. In the central basin, non-associated gases are produced mainly from Upper Mississippian and Pennsylvanian sandstones. Gas samples are from reservoirs as much as 6588 m deep. Gases become isotopically heavier (??13C1-values range from -49.8 to -33.2???) and chemically drier (C2+-values range from 1-33%) with increasing level of thermal maturity. Gases were generated mainly from interbedded shales with type-III kerogen during the mature and post-mature stages of hydrocarbon generation. Deviations from the trend are due to vertical migration and mixing of gases generated at different levels of thermal maturity over the past 250 Myr. In the giant Panhandle-Hugoton field, non-associated gases are generally produced from Permian carbonates at depths of <900 m. Gases display little compositional variation (mean ??13C1-value is -43.2???, mean C2+-value is 14%). Because organic-rich, mature source rocks are not present in the area, gases probably were generated in the central basin from Pennsylvanian or older source rocks during the mature stage of hydrocarbon generation. This interpretation implies migration over distances as much as several hundred kilometers. In the Sooner Trend, associated gases are produced from Silurian, Devonian and Mississippian carbonates at depths as great as 2950 m and were generated from type-II kerogen during the mature stage of hydrocarbon generation. Associated oil usually correlates with extracts of the Upper Devonian and Lower Mississippian Woodford Shale. Gases are isotopically lighter (mean ??13C1-value is -43.9???) and chemically wetter (mean C2+ value is 14%) than those derived from type-III kerogen at an equivalent level of thermal maturity. ?? 1988.

Chemical Geology↗

Carbon isotope geochemistry of hydrocarbons in the Cerro Prieto geothermal field, Baja California Norte, Mexico

Hydrocarbon abundances and stable-isotopic compositions were measured in wells M5, M26, M35 and M102, which represent a range of depths (1270-2000 m) and temperatures (275-330??C) in the field. In order to simulate the production of the geothermal hydrocarbons, gases were collected from the pyrolysis of lignite in the laboratory. This lignite was obtained from a well which sampled rock strata which are identical to those occurring in the field, but which have experienced much lower subsurface temperatures. In both the well and the laboratory observations, high-temperature environments favored higher relative concentrations of methane, ethane and benzene and generally higher ??13C-values in the individual hydrocarbons. The best correlation between the laboratory and well data is obtained when laboratory-produced gases from experiments conducted at lower (400??C) and higher (600??C) temperatures are mixed. This improved correlation suggests that the wells are sampling hydrocarbons produced from a spectrum of depths and temperatures in the sediments. ?? 1988.

Chemical Geology↗

Back-arc with frontal-arc component origin of Triassic Karmutsen basalt, British Columbia, Canada

The largely basaltic, ???4.5-6.2-km-thick, Middle to Upper Triassic Karmutsen Formation is a prominent part of the Wrangellian sequence. Twelve analyses of major and minor elements of representative samples of pillowed and massive basalt flows and sills from Queen Charlotte and Vancouver Islands are ferrotholeiites that show a range of 10.2-3.8% MgO (as normalized, H2O- and CO2-free) and related increases in TiO2 (1.0-2.5%), Zr (43-147 ppm) and Nb (5-16 ppm). Other elemental abundances are not related simply to MgO: distinct groupings are evident in Al2O3, Na2O and Cr, but considerable scatter is present in FeO* (FeO + 0.9Fe2O3) and CaO. Some of the variation is attributed to alteration during low-rank metamorphism or by seawater - including variation of Ba, Rb, Sr and Cu, but high-field-strength elements (Sc, Ti, Y, Zr and Nb) as well as Cr, Ni, Cu and rare-earth elements (REE's) were relatively immobile. REE's show chondrite-normalized patterns ranging from light-REE depleted to moderately light-REE enriched. On eleven discriminant plots these analyses fall largely into or across fields of within-plate basalt (WIP), normal or enriched mid-ocean-ridge tholeiite (MORB) and island-arc tholeiite (IAT). Karmutsen basalts are chemically identical to the stratigraphically equivalent Nikolai Greenstone of southern Alaska and Yukon Territory. These data and the fact that the Karmutsen rests on Sicker Group island-arc rocks of Paleozoic age suggest to us that: 1. (1) the basal arc, after minor carbonate-shale deposition, underwent near-axial back-arc rifting (as, e.g., the Mariana arc rifted at different times); 2. (2) the Karmutsen basalts were erupted along this rift or basin as "arc-rift" tholeiitite; and 3. (3) after subsequent deposition of carbonates and other rocks, and Jurassic magmatism, a large fragment of this basalt-sediment-covered island arc was accreted to North America as Wrangellia. The major- and minor-elemental abundances of Karmutsen basalt is modeled by first mixing primitive arc magma with enriched basaltic liquid derived either from garnet peridotite or metasomatized mantle, followed by fractionation of olivine, pyroxenes, plagioclase and spinel. ?? 1989.

Chemical Geology↗

Moderate-temperature zeolitic alteration in a cooling pyroclastic deposit

The locally zeolitized Topopah Spring Member of the Paintbrush Tuff (13 Myr.), Yucca Mountain, Nevada, U.S.A., is part of a thick sequence of zeolitized pyroclastic units. Most of the zeolitized units are nonwelded tuffs that were altered during low-temperature diagenesis, but the distribution and textural setting of zeolite (heulandite-clinoptilolite) and smectite in the densely welded Topopah Spring tuff suggest that these hydrous minerals formed while the tuff was still cooling after pyroclastic emplacement and welding. The hydrous minerals are concentrated within a transition zone between devitrified tuff in the central part of the unit and underlying vitrophyre. Movement of liquid and convected heat along fractures from the devitrified tuff to the ritrophyre caused local devitrification and hydrous mineral crystallization. Oxygen isotope geothermometry of cogenetic quartz confirms the nondiagenetic moderate temperature origin of the hydrous minerals at temperatures of ??? 40-100??C, assuming a meteoric water source. The Topopah Spring tuff is under consideration for emplacement of a high-level nuclear waste repository. The natural rock alteration of the cooling pyroclastic deposit may be a good natural analog for repository-induced hydrothermal alteration. As a result of repository thermal loading, temperatures in the Topopah Spring vitrophyre may rise sufficiently to duplicate the inferred temperatures of natural zeolitic alteration. Heated water moving downward from the repository into the vitrophyre may contribute to new zeolitic alteration. ?? 1989.

Chemical Geology↗

Metal and nutrient behavior in the Raritan estuary, New Jersey, U.S.A.: The effect of multiple freshwater and industrial waste inputs

A geochemical analysis of the Raritan estuary during high and low river flow is presented. Several statistical and graphical approaches, in addition to a hydrodynamic model of the Raritan estuary, are used to demonstrate the effects of lateral inputs on trace-element distribution in a complicated fluvial-marine system. Results from factor and cluster analysis show that nutrient-salinity distributions on both sampling dates are controlled primarily by freshwater-saltwater mixing. Industrial and municipal waste sources within the estuary are important in controlling dissolved organic carbon (at low flow) and dissolved and bottom sediment trace metals. Biological and physico-chemical reactions have a significant, but secondary effect on nutrient and trace-metal distributions with salinity. Apparent flux calculations and property-property plots show that for dissolved phosphate, nitrate and inorganic carbon, the Raritan estuary can be divided into two mixing zones, with the Raritan River controlling nutrient concentrations in the lower-salinity stretches and the South River controlling their distributions at intermediate and higher salinities. High enrichment factors of most metals in estuary bottom sediment reveal that this is an important and semi-permanent sink for trace metals in the Raritan system. Previous work on suspended sediment in the estuary and river substantiates that this load is also an important sink for trace metals; however, many of these metals are in leachable modes which are more susceptible to release and incorporation into the food chain. ?? 1990.

Chemical Geology↗

Activators of photoluminescence in calcite: evidence from high-resolution, laser-excited luminescence spectroscopy

Laser-excited luminescence spectroscopy of a red-algal, biogenic calcite and a synthetic Mn-calcite can make the distinction between organic and trace-element activators of photoluminescence. Organic-activated photoluminescence in biogenic calcite is characterized by significant peak shifts and increasing intensity with shorter-wavelength excitation and by significant decreases in intensity after heating to ??? 400??C. In contrast, Mn-activated photoluminescence shows no peak shift, greatest intensity under green excitation and limited changes after heating. Examination of samples with a high-sensitivity spectrometer using several wavelengths of exciting light is necessary for identification of photoluminescence activators. ?? 1990.

Chemical Geology↗

Subalkaline andesite from Valu Fa Ridge, a back-arc spreading center in southern Lau Basin: petrogenesis, comparative chemistry, and tectonic implications

Tholeiitic andesite was dredged from two sites on Valu Fa Ridge (VFR), a back-arc spreading center in Lau Basin. Valu Fa Ridge, at least 200 km long, is located 40-50 km west of the active Tofua Volcanic Arc (TVA) axis and lies about 150 km above the subducted oceanic plate. One or more magma chambers, traced discontinuously for about 100 km along the ridge axis, lie 3-4 km beneath the ridge. The mostly aphyric and glassy lavas had high volatile contents, as shown by the abundance and large sizes of vesicles. An extensive fractionation history is inferred from the high SiO2 contents and FeO* MgO ratios. Chemical data show that the VFR lavas have both volcanic arc and back-arc basin affinities. The volcanic arc characteristics are: (1) relatively high abundances of most alkali and alkaline earth elements; (2) low abundances of high field strength elements Nb and Ta; (3) high U/Th ratios; (4) similar radiogenic isotope ratios in VFR and TVA lavas, in particular the enrichment of 87Sr 86Sr relative to 206Pb 204Pb; (5) high 238U 230Th, 230Th 232Th, and 226Ra 230Th activity ratios; and (6) high ratios of Rb/Cs, Ba/Nb, and Ba/La. Other chemical characteristics suggest that the VFR lavas are related to MORB-type back-arc basin lavas. For example, VFR lavas have (1) lower 87Sr 86Sr ratios and higher 143Nd 144Nd ratios than most lavas from the TVA, except samples from Ata Island, and are similar to many Lau Basin lavas; (2) lower Sr/REE, Rb/Zr, and Ba/Zr ratios than in arc lavas; and (3) higher Ti, Fe, and V, and higher Ti/V ratios than arc lavas generally and TVA lavas specifically. Most characteristics of VFR lavas can be explained by mixing depleted mantle with either small amounts of sediment and fluids from the subducting slab and/or an older fragment of volcanic arc lithosphere. The eruption of subalkaline andesite with some arc affinities along a back-arc spreading ridge is not unique. Collision of the Louisville and Tonga ridges probably activated back-arc extension that ultimately led to the creation and growth of Valu Fa Ridge. Some ophiolitic fragments in circum-Pacific and circum-Tethyan allochthonous terranes, presently interpreted to have originated in volcanic arcs, may instead be fragments of lithosphere that formed during early stages of seafloor spreading in a back-arc basin. ?? 1991.

Chemical Geology↗

Modelling the petrogenesis of high Rb/Sr silicic magmas

Rhyolites can be highly evolved with Sr contents as low as 0.1 ppm and Rb Sr > 2,000. In contrast, granite batholiths are commonly comprised of rocks with Rb Sr < 10 and only rarely > 100. Mass-balance modelling of source compositions, differentiation and contamination using the trace-element geochemistry of granites are therefore commonly in error because of the failure to account for evolved differentiates that may have been erupted from the system. Rhyolitic magmas with very low Sr concentrations (???1 ppm) cannot be explained by any partial melting models involving typical crustal source compositions. The only plausible mechanism for the production of such rhyolites is Rayleigh fractional crystallization involving substantial volumes of cumulates. A variety of methods for modelling the differentiation of magmas with extremely high Rb/Sr is discussed. In each case it is concluded that the bulk partition coefficients for Sr have to be large. In the simplest models, the bulk DSr of the most evolved types is modelled as > 50. Evidence from phenocryst/glass/whole-rock concentrations supports high Sr partition coefficients in feldspars from high silica rhyolites. However, the low modal abundance of plagioclase commonly observed in such rocks is difficult to reconcile with such simple fractionation models of the observed trace-element trends. In certain cases, this may be because the apparent trace-element trend defined by the suite of cognetic rhyolites is the product of different batches of magma with separate differentiation histories accumulating in the magma chamber roof zone. ?? 1991.

Chemical Geology↗

A statistical approach to the interpretation of aliphatic hydrocarbon distributions in marine sediments

Q-mode factor analysis was used to quantitate the distribution of the major aliphatic hydrocarbon (n-alkanes, pristane, phytane) systems in sediments from a variety of marine environments. The compositions of the pure end members of the systems were obtained from factor scores and the distribution of the systems within each sample was obtained from factor loadings. All the data, from the diverse environments sampled (estuarine (San Francisco Bay), fresh-water (San Francisco Peninsula), polar-marine (Antarctica) and geothermal-marine (Gorda Ridge) sediments), were reduced to three major systems: a terrestrial system (mostly high molecular weight aliphatics with odd-numbered-carbon predominance), a mature system (mostly low molecular weight aliphatics without predominance) and a system containing mostly high molecular weight aliphatics with even-numbered-carbon predominance. With this statistical approach, it is possible to assign the percentage contribution from various sources to the observed distribution of aliphatic hydrocarbons in each sediment sample. ?? 1991.

Chemical Geology↗

Geochemistry of a Tertiary sedimentary phosphate deposit: Baja California Sur, Mexico

The San Gregorio Formation in Baja California Sur, a phosphate-enriched sedimentary unit of late Oligocene to early Miocene age, has been analyzed in two areas (La Purisima and San Hilario) for its chemical composition (major oxides, Cu, Cd, Cr, Co, V, and rare-earth elements - REE) and isotopic composition (??18O and ??13C). A detrital and a marine component were determined from major oxides. The detrital component consists of an unaltered volcanic-ash fraction and a terrigenous clay-silt fraction. The marine component, which accumulated initially as biogenic and hydrogenous material, is now present as opal-A, opal-CT, CaCO3, organic matter, and an authigenic phosphate fraction, mostly pelletal and composed of the carbonate-fluorapatite mineral francolite. The minor elements have been partitioned into these components by assuming a constant composition for the two detrital fractions. The composition of the marine component of minor elements can then be interpreted by assuming that the stoichiometry of the original accumulating organic matter was equal to that of modern plankton. The Cu and Cd contents in the marine component of all rocks require that the seawater-derived fractions of these two metals were supplied to the seafloor solely by organic matter. Enrichments of Cr and V at both sites required an additional marine input. On the basis of their geochemistry in the modern ocean, Cr and V could have precipitated, or been adsorbed, onto settling particles from an O2 minimum zone in which the O2 content was low enough to promote denitrification rather than oxygen respiration. An enrichment of the REE, now within the apatite fraction, resulted from their adsorption onto particulates also in the O2 minimum zone and to the dissolution and alteration of biogenic phases (predominantly silica) within the sediment. Co and Fe2O3 show no enrichment above a detrital contribution. The ??18O-values of apatites from the La Purisima site are heavier than those of apatites from the San Hilario site, whereas the ??13C-values show the opposite trend. One possible interpretation of these variations is that ??18O reflects seawater values and ??13C sediment pore water values. This interpretation suggests that upwelling rates and primary productivity within the water column were greater at La Purisima, an interpretation that is corroborated by a greater abundance of apatite measured in outcrop at La Purisima. The Ce anomalies of the phosphate-enriched samples also differ between the two sites, indicating that they also recorded water masses, similar to the ??18O-values. ?? 1991.

Chemical Geology↗

Vanadium accumulation in carbonaceous rocks: A review of geochemical controls during deposition and diagenesis

Published data relevant to the geochemistry of vanadium were used to evaluate processes and conditions that control vanadium accumulation in carbonaceous rocks. Reduction, adsorption, and complexation of dissolved vanadium favor addition of vanadium to sediments rich in organic carbon. Dissolved vanadate (V(V)) species predominate in oxic seawater and are reduced to vanadyl ion (V(IV)) by organic compounds or H2S. Vanadyl ion readily adsorbs to particle surfaces and is added to the sediment as the particles settle. The large vanadium concentrations of rocks deposited in marine as compared to lacustrine environments are the result of the relatively large amount of vanadium provided by circulating ocean water compared to terrestrial runoff. Vanadium-rich carbonaceous rocks typically have high contents of organically bound sulfur and are stratigraphically associated with phosphate-rich units. A correspondence between vanadium content and organically bound sulfur is consistent with high activities of H2S during sediment deposition. Excess H2S exited the sediment into bottom waters and favored reduction of dissolved V(V) to V(IV) or possibly V(III). The stratigraphic association of vanadiferous and phosphatic rocks reflects temporal and spatial shifts in bottom water chemistry from suboxic (phosphate concentrated) to more reducing (euxinic?) conditions that favor vanadium accumulation. During diagenesis some vanadium-organic complexes migrate with petroleum out of carbonaceous rocks, but significant amounts of vanadium are retained in refractory organic matter or clay minerals. As carbon in the rock evolves toward graphite during metamorphism, vanadium is incorporated into silicate minerals. ?? 1991.

Chemical Geology↗

Some Nd and Sr isotopic systematics for the REE-enriched deposit at Bayan Obo, China

Sm/1bNd and Rb/1bSr isotopic systematics have been determined for rare-earth element (REE) rich samples of carbonate, iron ore, and silicate types from the world's largest known REE deposit at Bayan Obo, China. The results yielded neither Rb/1bSr nor Sm/1bNd isochrons within analytical error. Isochronous relationships may have been disturbed in part by younger events. Modes in isotopic composition suggest two Sr reservoirs; the low 87Sr 86Sr ratios of 0.703 and 0.704 measured for two carbonates may be of mantle origin. The Sm/1bNd data delineate a trend at ??? 1 Ga; this trend might represent a disturbed fractionation event or mixing of Nd reservoirs. The REE ores could not have formed in a single fractionation event during the igneous activity at 260 Ma. Model ages suggest that the ore REE were isolated from mantle sources between ??? 1.7 and ??? 1.3 Ga. This time period hosts major anorogenic igneous activity, including anorthosites, and a number of other unusual REE iron ores. ?? 1991.

Chemical Geology↗