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USGS1992

Chemical changes and carbon isotope variations in a cross-section of a large Miocene gymnospermous log

The cross-sectional radius of a 3-m (diam.) brown coal gymnospermous log of Miocene age, previously analyzed for carbohydrate and lignin methoxyl content by solid-state 13 C nuclear magnetic resonance spectroscopy, was examined using stable carbon isotopic ratios in order to determine if the isotopic composition could be related to chemical changes or to radial position. This study found a possible relationship between δ 13 C-values and radial position; however, these changes cannot be linked to carbohydrate content and are probably attributable to changing growth conditions during the lifetime of the tree. An apparent linear relationship between the changes in carbohydrate content after sodium para-periodate treatment and corresponding changes in the δ 13 C-values indicates constant isotopic fractionation between lignin and carbohydrates along the cross-sectional radius. This result indicates that diagenesis has not produced any significant change in the lignin-carbohydrate carbon isotopic fractionation or, alternatively, that diagenesis has erased any fractionation pattern that once existed. A sample of fresh wood from another gymnospermous species was analyzed by the same methods and found to have lignin-carbohydrate carbon isotopic fractionation significantly different from that of the Miocene log section samples, suggesting that differences may be species-related or that the complex mixture of carbohydrates in the fresh wood was isotopically different from that of the degraded wood, and the whole Miocene log was uniformly altered.

Chemical Geology↗
USGS1992

Gold deposition by sulfidation of ferrous Fe in the lacustrine sediments of the Pueblo Viejo district (Dominican Republic): The effect of Fe-C-S diagenesis on later hydrothermal mineralization in a Maar-Diatreme complex

The Pueblo Viejo district, located in the Cordillera Central of the Dominican Republic, contains large Au-Ag deposits associated with acid-sulfate alteration within spilites, conglomerates and carbonaceous sedimentary rocks that were deposited in a maar-diatreme complex. Much of the Au mineralization occurs in pyritic, carbonaceous siltstones of the Pueblo Viejo Maar-Diatreme Member of the Cretaceous Los Ranchos Formation. Pyrite is the only Fe-bearing phase in mineralized rock, whereas siderite is the dominant Fe-bearing phase in siltstones distal to mineralization. Disseminated pyrite occurs as framboids, cubes, pyritohedra, concretions and cement. Early framboids occur throughout the district. Au occurs as inclusions in later non-framboid disseminated pyrite (NFDP); an occurrence that is interpreted to be indicative of contemporaneous deposition. Pyrite framboids exhibit a wide range of ??34Scdt-values (-17.5 to +4.8???) and are interpreted to have formed during biogenic reduction of pore-water sulfate. The NFDP yield restricted ??34Scdt-values ( x ?? = -5.2???, s = ??2.4???, n = 43) similar to those obtained from later vein pyrite ( x ?? = -6.4???, s = ??1.5???, n = 12). Alunite and barite have ??34S-values ranging from +18.8 to +21.6???. The interpretation that the NFDP, vein pyrite, alunite and barite, and possibly even the framboidal pyrite share a common source of igneous sulfur is supported by the ??34S data. Siderite occurs as concretions and cement, contains abundant Mg (Fe0.75Mg0.19Mn0.03Ca0.02CO3) and has ??13Cpdb- and ??18Osmow-values ranging from -2.5 to +1.1%. and +14.6 to +19.5???, respectively. These data are consistent with the interpretation that the siderite formed in lacustrine sediments and that the carbonate in the siderite is probably methanogenic, although contributions from oxidation of organic matter during biogenic sulfate reduction, thermal decarboxylation of organic matter, or magmatic vapor cannot be ruled out. Disseminated Au mineralization in the sedimentary rocks formed when a hydrothermal fluid encountered reactive Fe2+ in diagenetic siderite. The ensuing pyrite deposition consumed H2S and destabilized the Au (HS)-2 complex, leading to precipitation of Au. The capacity of the sedimentary rocks to consume H2S and precipitate Au was controlled by the amount of non-pyrite Fe present as siderite. The abundance of siderite was controlled by the extent of pyrite formation during diagenesis. ?? 1992.

Chemical Geology↗
USGS1992

Relationship between inferred redox potential of the depositional environment and geochemistry of the Upper Pennsylvanian (Missourian) Stark Shale Member of the Dennis Limestone, Wabaunsee County, Kansas, U.S.A.

Analyses of 21 samples collected from a core of the 52.8-cm-thick Stark Shale Member of the Dennis Limestone in Wabaunsee County, Kansas, demonstrate four cycles with two-orders-of-magnitude variations in contents of Cd, Mo, P, V and Zn, and order-of-magnitude variations in contents of organic carbon, Cr, Ni, Se and U. The observed variability in amounts and/or ratios of many metals and amounts and compositions of the organic matter appear related to the cause and degree of water-column stratification and the resulting absence/presence of dissolved O2 or H2S. High Cd, Mo, U, V, Zn and S contents, a high degree of pyritization (DOP) (0.75-0.88), and high high V (V + Ni) (0.84-0.89) indicate the presence of H2S in a strongly stratified water column. Intermediate contents of metals and S, intermediate DOP (0.67-0.75) and intermediate V (V + Ni) (054-0.82) indicate a less strongly stratified anoxic water column. Whereas, low metal contents and low V (V + Ni) (0.46-0.60) indicate a weakly stratified, dysoxic water column. High P contents at the top of the organic-matter-rich intervals within the Stark Shale Member indicate that phosphate precipitation was enhanced near the boundary between anoxic and dysoxic water compositions. Relatively abundant terrestrial organic matter in intervals deposited from the more strongly stratified H2S-bearing water column indicates a combined halocline-thermocline with the fresher near-surface water the transport mode for the terrestrial organic matter. The predominance of algal organic matter in intervals deposited from a less strongly stratified water column indicates the absence of the halocline and the presence of the more generally established thermocline. Relatively low amounts of degraded, hydrogen-poor organic matter characterize intervals deposited in a weakly stratified, dysoxic water column. The inferred variability in chemistry of the depositional environments may be related to climate variations and/or minor changes in sea level during the general phase of deeper water deposition responsible for this widespread shale member. ?? 1992.

Chemical Geology↗
USGS1992

Gold and platinum in shales with evidence against extraterrestrial sources of metals

Few black shales contain concentrations of precious metals higher than average continental crust (i.e. ???5 ppb Au). Yet Au and Pt alloys have been reported from the Kupferschiefer in Poland. Moreover, thin sulfide beds in certain Chinese and Canadian shales contain several hundred ppb Au, Pd and Pt and average ???4% Mo and ???2.5% Ni in an association that is difficult to explain. Volcanic and non-volcanic exhalations, hydrothermal epigenesis involving either igneous or sedex fluids, biogenic processes and low-temperature secondary enrichment are among the possible factors involved in deriving Ni, PGE and Au for black shales and sulfide beds in black shales. Extraterrestrial sources have been invoked in some cases (e.g., the Cambrian of China). However, available data on abundances of PGE indicate relatively low values for Ir (<0.02-2 ppb) in comparison with amounts for other PGE (up to 700 ppb Pt and 1255 ppb Pd). These data and high contents for Mo are not consistent with extraterrestrial sources of metals for Chinese shales and Ni-Mo-sulfide beds. Data are less complete for the U.S. shales, but nevertheless are suggestive of earthly origins for PGE. ?? 1992.

Chemical Geology↗
USGS1992

Chemical fluxes and origin of a manganese carbonate-oxide-silicate deposit in bedded chert

Lens-like rhodochrosite-rich bodies within interbedded chert and shale are associated with basalt and/or graywacke in ophiolitic and orogenic zones. The Buckeye manganese mine in the Franciscan Complex of the California Coast Ranges is associated with metagraywacke. Despite blueschist-facies metamorphism, this deposit preserves the compositions and some textural features of its sedimentary protoliths. For this reason, it is a suitable deposit with which to compare more intensely altered deposits, or deposits originating in different paleoenvironments. Six Mn-rich and three Mn-poor minerals form monomineralic layers and mixtures: rhodochrosite, gageite, Mn-oxides (hausmannite, braunite), divalent Mn-silicates (caryopilite, taneyamalite), chlorite, quartz (metachert) and aegirine-augite. The Mn-rich protoliths have high Mn/Fe combined with relatively low concentrations of Ca, Al, Ti, Co, Ni, Cu, Th and REE. REE patterns of various protoliths are distinct. Rhodochrosite and gageite layers are depleted (seawater ?? 5 ?? 104) and flat, whereas patterns of metachert and the Mn-silicate-rich layers mimic the patterns of metashale and metagraywacke (seawater ?? 106). Hausmannite layers have flat patterns (seawater ?? 7 ?? 104) whereas braunite-rich layers are more enriched (seawater ?? 2 ?? 105) and show a distinct positive Ce anomaly. Factor analysis reveals components and fluxes attributed to sub-seafloor fluids (Ni, As, Zn, Sb, W, Mn), seawater (Mg, Au, V, Mo), detritus and veins (Ca, Ba, Sr). Silica is negatively correlated with the sub-seafloor factor. The observed variances indicate that water from the sediment column mixed with seawater, that deposition occurred near the sediment-seawater interface before mixtures of subsurface fluid and seawater homogenized, and that the system was not entirely closed during metamorphism. The variations in REE enrichment can be related to kinetics of deposition: rhodochrosite and gageite were precipitated most rapidly, and therefore were the protoliths that most effectively diluted the REE-rich background resulting from fine clastic material (derived from distal turbidites). The variation of the Ce anomaly and U/Th among diverse lithologies and the differences in Mn oxidation states are consistent with progressive dilution of reduced subsurface fluids with oxidized seawater. By this scheme, rhodochrosite, gageite and hausmannite were deposited from the most reduced fluids, braunite from intermediate mixtures, and Mn-silicates from the sub-seafloor fluids most diluted with fresh seawater. Comparison of the Buckeye with other lens-like and sheet-like deposits having high Mn/Fe and containing Mn3+ and/or Mn2+ suggests that each had three essential fluxes: a sub-seafloor source of Mn, a local source of very soluble silica and a source of relatively fresh, oxygenated water. Additional fluxes, such as clastics, appear to be more characteristic of the paleoenvironment than the three essential fluxes. ?? 1992.

Chemical Geology↗
USGS1992

Comparison of methods for the removal of organic carbon and extraction of chromium, iron and manganese from an estuarine sediment standard and sediment from the Calcasieu River estuary, Louisiana, U.S.A.

U.S. National Bureau of Standards (NBS) estuarine sediment 1646 from the Chesapeake Bay, Maryland, and surface sediment collected at two sites in the Calcasieu River estuary, Louisiana, were used to evaluate the dilute hydrochloric acid extraction of Cr, Fe and Mn from air-dried and freeze-dried samples that had been treated by one of three methods to remove organic carbon. The three methods for the oxidation and removal of organic carbon were: (1) 30% hydrogen peroxide; (2) 30% hydrogen peroxide plus 0.25 mM pyrophosphate; and (3) plasma oxidation (low-temperature ashing). There was no statistically significant difference at the 95% confidence level between air- and freeze-dried samples with respect to the percent of organic carbon removed by the three methods. Generally, there was no statistically significant difference at the 95% confidence level between air- and freeze-dried samples with respect to the concentration of Cr, Fe and Mn that was extracted, regardless of the extraction technique that was used. Hydrogen peroxide plus pyrophosphate removed the most organic carbon from sediment collected at the site in the Calcasieu River that was upstream from industrial outfalls. Plasma oxidation removed the most organic carbon from the sediment collected at a site in the Calcasieu River close to industrial outfalls and from the NBS estuarine sediment sample. Plasma oxidation merits further study as a treatment for removal of organic carbon. Operational parameters can be chosen to limit the plasma oxidation of pyrite which, unlike other Fe species, will not be dissolved by dilute hydrochloric acid. Preservation of pyrite allows the positive identification of Fe present as pyrite in sediments.

Chemical Geology↗
USGS1992

Chemical, crystallographic and stable isotopic properties of alunite and jarosite from acid-Hypersaline Australian lakes

Chemical, crystallographic and isotopic analyses were made on samples containing alunite and jarosite from the sediments of four acid, hypersaline lakes in southeastern and southwestern Australia. The alunite and jarosite are K-rich with relatively low Na contents based on chemical analysis and determination of unit cell dimensions by powder X-ray diffraction. Correcting the chemical analyses of fine-grained mineral concentrates from Lake Tyrrell, Victoria, for the presence of halite, silica and poorly crystalline aluminosilicates, the following formulas indicate best estimates for solid-solution compositions: for alunite, K 0.87 Na 0.04 (H 3 O) 0.09 (Al 0.92 Fe 0.08 ) 3 (SO 4 ) 2 (OH) 6 and for jarosite, K 0.89 Na 0.07 (H 3 O) 0.04 (Fe 0.80 Al 0.20 ) 3 (SO 4 ) 2 (OH) 6 . The δD-values of alunite are notably larger than those for jarosite from Lake Tyrrell and it appears that the minerals have closely approached hydrogen isotope equilibrium with the acidic regional groundwaters. The δD results are consistent with a fractionation ∼60–70‰ between alunite and jarosite observed in other areas. However, interpretation of δD results is complicated by large variability in fluid δD H2O from evaporation, mixing and possible ion hydration effects in the brine. δD-values of water derived from jarosite by step-wise heating tend to be smaller at 250°C, at which temperature hydronium and other non-hydroxyl water is liberated, than at 550°C, where water is derived from the hydroxyl site, but the differences are not sufficiently different to invalidate measurements of total δD obtained by conventional, single-step heating methods. δ 34 S-values for alunite and jarosite from the four lakes (+19.7 to +21.2‰ CDT) and for aqueous sulfate from Lake Tyrrell (+18.3 to +19.8‰) are close to the values for modern evaporites ( +21.5 &#xB1;0.3&#x2030; ">‰ +21.5 ±0.3‰ ) and seawater ( +20&#xB1;0.5&#x2030; ">‰ +20±0.5‰ ) and are probably typical of seawater-derived aerosols in arid coastal environments. δ 34 -S-values slightly smaller than that for seawater may reflect a minor contribution of sulfate from pyrite oxidation in the Parilla Sand or a reservoir effect from removal of gypsum enriched in 34 S. δ 18 O SO4 -values for alunite from three Western Australia lakes (+17.8 to +18.3‰ V-SMOW), for alunite and jarosite from Lake Tyrrell (+22.6 to +24.9‰) and for aqueous sulfate from Lake Tyrrell (+17.3 to +19.0‰) are much larger than the average value for seawater (+9.6‰). The data suggest an approach to 18 O- 16 O equilibrium between aqueous sulfate and groundwater, which is known from experimental studies to be possible at low pH and low temperatures, but has not been previously documented in nature. A residence time of ∼0.1–1 kyr for sulfate in acidic water (pH 3–4) is needed to achieve the apparent partial oxygen exchange, using previously published data of R.M. Lloyd.

Chemical Geology↗
USGS1992

Mechanisms of iron photoreduction in a metal-rich, acidic stream (St. Kevin Gulch, Colorado, U.S.A.)

Iron photoreduction in metal-rich, acidic streams affected by mine drainage accounts for some of the variability in metal chemistry of such streams, producing diel variations in Fe(II). Differentiation of the mechanisms of the Fe photoreduction reaction by a series of in-stream experiments at St. Kevin Gulch, Colorado, indicates that a homogeneous, solution-phase reaction can occur in the absence of suspended particulate Fe and bacteria, and the rate of reaction is increased by the presence of Fe colloids in the stream water. In-stream Fe photoreduction is limited during the diel cycle by the available Fe(III) in the water column and streambed. The quantum yield of Fe(II) was reproducible in diel measurements: the quantum yield, in mol E-1 (from 300 to 400 nm) was 1.4 ?? 10-3 in 1986, 0.8 ?? 10-3 in 1988 and 1.2 ?? 10-3 in 1989, at the same location and under similar streamflow and stream-chemistry conditions. In a photolysis control experiment, there was no detectable production of Fe(II) above background concentrations in stream-water samples that were experimentally excluded from sunlight. ?? 1992.

Chemical Geology↗
USGS1993

The analysis of forms of sulfur in ancient sediments and sedimentary rocks: comments and cautions

Assumptions commonly made during analysis of the amount of monosulfides [acid-volatile sulfides (AVS)] and disulfides in modern sediments, may not be valid for ancient sedimentary rocks. It is known that ferric iron can oxidize H2S during AVS analysis unless a reducing agent such as stannous chloride is added to the treatment. In addition, some monosulfides such as greigite and pyrrhotite require heat during the AVS analysis in order to dissolve completely. However, the use of heat and/or stannous chloride in the AVS treatment may partially dissolve disulfides and it is generally recommended that stannous chloride not be used in the AVS treatment for modern sediments. Most of the monosulfides are assumed to be recovered as AVS without the addition of stannous chloride. This study investigates the recovery of monosulfides during sulfur speciation analysis with application to ancient sedimentary rocks. Sulfur in samples containing naturally occurring greigite and mackinawite or pyrite was measured using variations of a common sulfur-speciation scheme. The sulfur-speciation scheme analyzes for monosulfide sulfur, disulfide sulfur, elemental sulfur, inorganic sulfate and organically bound sulfur. The effects of heat, stannous chloride and ferric iron on the amounts of acid-volatile sulfide and disulfide recovered during treatment for AVS were investigated. Isotopic compositions of the recovered sulfur species along with yields from an extended sulfur-speciation scheme were used to quantify the effects. Hot 6 N HCl AVS treatment recovers > 60% of the monosulfides as AVS in samples containing pure greigite and mackinawite. The remaining monosulfide sulfur is recovered in a subsequent elemental sulfur extraction. Hot 6 N HCl plus stannous chloride recovers 100% of the monosulfides as AVS. The addition of ferric iron to pure greigite and mackinawite samples during AVS treatment without stannous chloride decreased the amount of monosulfides recovered as AVS and, if present in great enough concentration, oxidized some of the AVS to a form not recovered in later treatments. The hot stannous chloride AVS treatments dissolve <5% of well-crystallized pyrite in this study. The amount of pyrite dissolved depends on grain size and crystallinity. Greigite in ancient sedimentary rocks was quantitatively recovered as AVS only with hot 6 N HCl plus stannous chloride. Hot 6 N HCl AVS treatment of these rocks did not detect any monosulfides in most samples. A subsequent elemental sulfur extraction did not completely recover the oxidized monosulfides. Therefore, the use of stannous chloride plus heat is recommended in the AVS treatment of ancient sedimentary rocks if monosulfides are present and of interest. All assumptions about the amount of monosulfides and disulfides recovered with the sulfur-speciation scheme used should be verified by extended sulfur-speciation and/or isotopic analysis of the species recovered. ?? 1993.

Chemical Geology↗
USGS1993

Epigenetic sulfide mineralization associated with Pennsylvanian paleokarst in eastern Iowa, U.S.A.

Paleokarst-associated, sulfide-bearing mineral deposits are wide-spread in the Paleozoic carbonate rocks of eastern Iowa. Minerals occur in nodules enclosed in karst-filling mudstones, as sandstone cements, and as surface coatings on, and fracture fillings in, foundered carbonate rock clasts. Mineralogy and paragenetic sequence vary among the occurrences. Sulfur isotopic compositions exhibit wide variations within and among deposits (??34S = -33.8 to + 35.1???). Oxygen isotopic compositions of fracture-filling calcite spars (??18O = -8.41 to + 3.60???) are similar to the isotopic compositions of their carbonate rock hosts. Calcite spars are somewhat depleted in ??13C relative to host rock [??13C (spars) = - 5.66 to + 0.24??? vs. -1.54 to + 1.21??? (host rock)]. Results of mineralogic, paragenetic and isotopic investigations suggest that: (1) minerals are products of multiple events operating on a local, rather than a regional scale; (2) spatially-disjunct fracture-filling mineral deposits exposed in the same quarries are probably not cogenetic with paleokarst-associated deposits; (3) paleokarst-filling calcite spars formed at near-surface temperatures; and (4) paleokarst-associated deposits are probably not cogenetic with Upper Mississippi Valley ZnPb pitch-flat deposits. ?? 1993.

Chemical Geology↗
USGS1993

Speciation and isotopic composition of sulfur in sediments from Jellyfish Lake, Palau

Jellyfish Lake, Palau, is a meromictic marine lake with high organic productivity, low reactive Fe content, and anoxic bottom waters. Sediment samples from Jellyfish Lake were examined for the distribution of sulfur species and their isotopic signatures in order to gain a better understanding of sedimentary sulfur incorporation in Fe-poor environments. Surface samples were taken along a transect from a near-shore site to the center of the lake, and include a sample below oxic water, a sample below the chemocline layer, and samples below anoxic waters. Three additional samples were taken from a core, 2 m long, collected near the lake center. Sulfur to organic carbon weight ratios in all samples were lower than the expected value of 0.36 for normal marine sediment, probably because the lake water is deficient in reactive Fe to form iron sulfides. Total sulfur contents in the surface sediments indicated no changes with distance from shore; however, the sulfur content of the surface sample at the chemocline layer may be slightly higher. Total sulfur content increased with depth in the core and is inversely related to organic carbon content. Organic sulfur is the major sulfur species in the samples, followed in descending order by sulfate, disulfides and monosulfides. Sulfate sulfur isotope ??34S-values are positive (from +20.56 to +12.04???), reflecting the marine source of sulfate in Jellyfish Lake. Disulfide and monosulfide ??34S-values are negative (from -25.07 to -7.60???), because of fractionation during bacterial reduction of sulfate. Monosulfide ??34S-values are somewhat higher than those of disulfides, and they are close to the ??34S-values of organic sulfur. These results indicate that most of the organic sulfur is formed by reaction of bacteriogenic monosulfides, or possibly monosulfide-derived polysulfides, with organic matter in the sediment. ?? 1993.

Chemical Geology↗
USGS1993

Hydrologic, chemical, and isotopic characterization of two small watersheds on Catoctin Mountain, north-central Maryland, U.S.A.

Two small (100 ha) watersheds located on Catoctin Mountain in north-central Maryland were intensively instrumented in 1990 and have been hydrologically, chemically, and isotopically monitored for 3 years. Dissolved concentrations of major ions (Ca 2+ , Mg 2+ , Na + , K + , total AI, CI - , NO 3 - , SO 4 2- , HCO 3 - , and SiO 2 ) and stable isotopic (D and 18 O) values have been analyzed for most types of water (precipitation, throughfall, two depths of soil water, shallow groundwater, and streamwater) that enter, travel through, and exit each watershed. The major objectives of the study were to characterize the chemical and isotopic signatures of all aqueous components of the watersheds and to interpret the causes of the changes in chemical and isotopic compositions of streamwater during storm runoff. This paper describes selected results of the study.

Maryland↗
USGS1993

Monazite paragenesis and U-Pb systematics in rocks of the eastern Mojave Desert, California, U.S.A.: implications for thermochronometry

Studies of the paragenesis and U-Pb systematics of monazite in rocks from the eastern Mojave Desert, California, corroborate its potential usefulness as a prograde thermochronometer and in dating granite inheritance. Unmetamorphosed Latham Shale and its equivalents at grades ranging from greenschist to upper amphibolite facies are virtually identical in composition. Monazite is absent in the shale and low-grade schists, but it is abundant in schists at staurolite and higher grades. Lower-grade schists instead include minute Th- and Ce-oxides and unidentified Ce-poor LREE-phosphates that apparently are lower-temperature precursors to monazite. Thus monazite originates when the pelite passes through lower-amphibolite-facies conditions. Monazites from three Upper Cretaceous granites yield ages that are strongly discordant. Upper intercepts of 1.6-1.7 Ga are similar to those defined by U-Pb data for coexisting zircons and coincide with a period of copious magmatism in the Mojave crust. As the host Upper Cretaceous granitic magmas were all above 700??C, effective closure of the restitic monazites to Pb loss must be well in excess of this temperature. U-Pb compositions of monazite from Proterozoic granitoids and schist also indicate high Pb retentivity. Taken together, these studies support the suggestion that monazite can be an effective prograde thermochronometer. At least in pelites, it is not usually retained as a detrital mineral, but rather forms during moderate-temperature metamorphism. Its U-Pb system should not be reset by subsequent higher-grade metamorphism. ?? 1993.

Chemical Geology↗
USGS1995

Sulfur geochemistry of organic-rich sediments from Mud Lake, Florida, USA

The cores include the upper 4 m of sediment, which consist of four major horizons based on petrographic analyses of the organic material. Systematic changes in the isotopic composition of sedimentary disulfide and organic sulfur coincide with variations in the sulfur species and vegetation types. The transition to sapropel is accompanied by a large negative shift in disulfide ??34S- values, consistent with an increase in sulfate availability and a slower rate of sulfate reduction. -from Authors

Chemical Geology↗
USGS1994

Seawater as the source of minor elements in black shales, phosphorites and other sedimentary rocks

Many of the minor elements in seawater today have a concentration-depth profile similar to that of the biologically essential nutrients, NO-3 and PO3-4. They show a relative depletion in the photic zone and enrichment in the deep ocean. The difference between their surface- and deep-ocean values, normalized to the change in PO3-4, approaches the average of measured minor-element: P ratios in marine plankton, although individual analyses of the latter show extreme scatter for a variety of reasons. Despite this scatter in the minor-element analyses of plankton, agreement between the two sets of data shows unequivocally that an important marine flux of many minor elements through the ocean is in the form of biogenic matter, with a composition approaching that of plankton. This interpretation is further supported by sediment studies, particularly of sediments which accumulate in shelf-slope environments where biological productivity in the photic zone is exceptionally high and organic carbon contents of the underlying sediment elevated. The interelement relations observed for some of these sediments approach the average values of plankton. These same interelement relations are observed in many marine sedimentary rocks such as metalliferous black shales and phosphorites, rocks which have a high content of marine fractions (e.g., organic matter, apatite, biogenic silica and carbonates). Many previous studies of the geochemistry of these rocks have concluded that local hydrothermal activity, and/or seawater with an elemental content different from that of the modern ocean, was required to account for their minor-element contents. However, the similarity in several of the minor-element ratios in many of these formations to minor-element ratios in modern plankton demonstrates that these sedimentary rocks accumulated in environments whose marine chemistry was virtually identical to that seen on continental shelf-slopes, or in marginal seas, of the ocean today. The accumulation of the marine fraction of minor elements on these ancient sea floors was determined largely by the accumulation of organic matter, settling from the photic zone and with a composition of average plankton. A second marine fraction of minor elements in these rocks accumulated through precipitation and adsorption from seawater. The suite of elements in this fraction reflects redox conditions in the bottom water, as determined by bacterial respiration. For example, high Mn, high Cr+V and high Mo concentrations, above those which can be attributed to the accumulation of planktonic matter, characterize accumulation under bottom-water oxidizing, denitrifying and sulfate-reducing conditions, respectively. ?? 1994.

Chemical Geology↗
USGS1994

Isotopic evidence for the source of sulfur in the Upper Freeport coal bed (west-central Pennsylvania, U.S.A.)

Sulfur isotopic variations were used to determine the sources of sulfur in a medium-sulfur coal (???2 wt%S) that lacked marine influence, which is often cited as a major source of sulfur in coal. Variations in the amount and isotopic composition of the organic and pyritic sulfur among the coal-bed facies of the Upper Freeport coal bed (Middle Pennsylvanian) are attributed to differential incorporation of syngenetic and epigenetic sulfur. These variations reflect varying environmental conditions during paleopeat formation, porosity and permeability, and the availability of sulfate and iron. A large increase in the abundance and sulfur isotopic value of pyritic sulfur in the upper facies of the coal bed, in proximity to the overlying lacustrine shale, corresponds to an increase in massive and irregular forms of pyrite. This relationship is attributed to at least two stages of epigenetic pyrite incorporation. An early stage of epigenetic pyrite, moderately enriched in 34S, apparently formed during the fluvial-lacustrine period immediately following peat accumulation. A late stage of epigenetic pyrite, highly enriched in 34S, formed after compaction of the original peat as cleat- and fracture-filling pyrite; this sulfur was probably derived from bacterial reduction of dissolved sulfate in groundwater. Isotopic mass-balance calculations indicate that this late-stage epigenetic pyrite may account for up to ???50% of the pyritic sulfur in some upper facies of the coal bed. These results suggest that most of the pyritic sulfur in the Upper Freeport coal bed may be epigenetic, incorporated either soon after peat accumulation or later during coalification. ?? 1994.

Chemical Geology↗
USGS1994

Sources of dissolved salts in the central Murray Basin, Australia

Large areas of the Australian continent contain scattered saline lakes underlain by shallow saline groundwaters of regional extent and debated origin. The normative salt composition of subsurface pore fluids extracted by squeezing cores collected during deep drilling at Piangil West 2 in the central Murray Basin in southeastern Australia, and of surface and shallow subsurface brines produced by subaerial evaporation in the nearby Lake Tyrrell systems, helps constrain interpretation of the origin of dissolved solutes in the groundwaters of this part of the continent. Although regional sedimentation in the Murray Basin has been dominantly continental except for a marine transgression in Oligocene-Pliocene time, most of the solutes in saline surface and subsurface waters in the central Murray Basin have a distinctly marine character. Some of the Tyrrell waters, to the southwest of Piangil West 2, show the increase in NaCl and decrease in sulfate salts expected with evaporative concentration and gypsum precipitation in an ephemeral saline lake or playa environment. The salt norms for most of the subsurface saline waters at Piangil West 2 are compatible with the dilution of variably fractionated marine bitterns slightly depleted in sodium salts, similar to the more evolved brines at Lake Tyrrell, which have recharged downward after evaporation at the surface and then dissolved a variable amount of gypsum at depth. Apparently over the last 0.5 Ma significant quantities of marine salt have been blown into the Murray Basin as aerosols which have subsequently been leached into shallow regional groundwater systems basin-wide, and have been transported laterally into areas of large evaporative loss in the central part of the basin. This origin for the solutes helps explain why the isotopic compositions of most of the subsurface saline waters at Piangil West 2 have a strong meteoric signature, whereas the dissolved salts in these waters appear similar to a marine assemblage. ?? 1994.

Chemical Geology↗