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USGS1993

Actualistic models of mantle metasomatism documented in a composite xenolith from Dish Hill, California

Major and trace-element whole rock and mineral variations in composite hornblendite-peridotite xenolith Ba-2-1, from Dish Hill, CA, are due to a single event of metasomatism in the mantle. The hornblendite is the crystallized selvage of a dike conduit charged with incompatible-element-enriched hydrous mafic magma. The magma infiltrated the refractory peridotite wallrock, reacted with its constituent minerals, and simultaneously deposited amphibole. The systematic data from this study show considerable variation in isotopic values and trace elements. These data provide insight into a mantle process that was defined previously from samples without context, lacking evidence about the number or source of metasomatic events. In the contact zone of Ba-2-1, peridotite is enriched in Fe, Ti, CO 2 ) and H 2 O; clinopyroxene and amphibole also are enriched in Fe and Ti, but clinopyroxene appears slightly depleted in CaO. Compared to chondrites, peridotite, clinopyroxene, and probably amphibole are enriched in light rare earth (LREE cn ) and other incompatible trace elements. Values of 87 Sr 86 Sr "> 87 Sr 86 Sr and 143 Nd 144 Nd "> 143 Nd 144 Nd in the contact zone are close to isotopic equilibrium with the dike. Whole rock and constituent clinopyroxene compositions change to those of refractory peridotite with distance from the contact. These compositional variations were modelled using Gresens' equation for whole-rock major and minor elements, and calculations for isotopic ratios and REEs, which emulate the effects of Chromatographic fractionation. The choice of endmembers was restricted to compositions actually present in mantle samples from Dish Hill. Model results indicate that: 1. the variations can be explained as the result of a single metasomatic event, probably a single pulse of previously fractionated liquid; 2. the ratio of total interacting liquid to peridotite was at least 1:3 by weight in the contact zone; and 3. the composition of the metasomatic liquid changed progressively as it infiltrated beyond that zone. The small distance over which variations occur is due to the small amount of liquid that infiltrated. Only in the contact zone was peridotite wallrock saturated by a liquid composition similar to the dike. Comparison of the Ba-2-1 data with those of another xenolith from Dish Hill suggests that the compositional variations of mantle metasomatism result from both the compositional contrast between the metasomatizing liquid and wallrock and the relative abundances of each. Compositional and volumetric variations of mantle partial melts and their fractionates, and repeated events of melting and reaction in contiguous mantle, can create broad ranges of metasomatic “signatures” from the same process.

California↗

USGS1993

Thermal stability of hydrocarbons in nature: Limits, evidence, characteristics, and possible controls

Numerous petroleum-geochemical analyses of deeply buried, high-rank, fine-grained rocks from ultra-deep wellbores by different investigators demonstrate that C 15 + hydrocarbons (HCs) persist in moderate to high concentrations at vitrinite reflectance ( R 0 ) values of 2.0–5.0% and persist in measurable concentrations up to R 0 = 7.0–8.0%, at which point the thermal deadline for C 15 + HC's is finally approached. Qualitative analyses have been carried out on 1. (1) high-rank gas condensates which have been exposed to the HC-thermal-destructive phase, 2. (2) bitumens from high-temperature aqueous-pyrolysis experiments in the HC-thermal-destructive phase, and 3. (3) bitumens from high-rank, fine-grained rocks near the HC-thermal-destructive phase. These analyses clearly demonstrate that well-defined compositional suites are established in the saturated, aromatic, and sulfur-bearing aromatic HCs in and near the HC-thermal-destructive phase. On the other hand, accepted petroleum-geochemical paradigms place rigid limits on HC thermal stability: C 15 + HCs begin thermal cracking at R 0 values of 0.9% and are completely thermally destroyed by R 0 = 1.35%; C 2 -C 4 HC gases are thermally destroyed by R 0 = 2.0% and methane is thermally destroyed by R 0 = 4.0%. Furthermore, published data and observations in many HC basins worldwide support these models; for example, 1. (1) sharp basinal zonations of gas and oil deposits vs. maturation rank in HC basins and 2. (2) decreasing C 15 + HC concentrations in some fine-grained rocks at ranks of R 0 ≥ 0.9%. The fact that observed data (C 15 + HCs thermally stable to R 0 = 7.0–8.0%) is so far removed from predicted behavior (C 15 + ) HCs expected to be thermally destroyed by R 0 = 1.35%) may be due to 1. (1) a lack of recognition of some important possible controlling parameters of organic matter (OM) metamorphism and too much importance given to other assumed controlling parameters; and 2. (2) assigning HC distribution patterns in petroleum basins to HC thermal cracking when such patterns may be due to other causes. In the first case, laboratory experiments strongly suggest that the presence of water, increasing fluid pressures, and closed systems (product retention) all suppress OM metamorphic reactions. Conversely, the absence of water, low fluid pressures, and open systems (product escape) all promote OM metamorphic reactions. These experiments also demonstrate that OM metamorphic reactions proceed by reaction kinetics greater than first order. Thus, the effect of geologic time appears to have been over-estimated in OM metamorphism. In the second case, the strong decreases in C 15 + HC concentrations in fine-grained rocks with Type III OM over R 0 = 0.9−1.35% are most probably due to intense primary migration and loss of HCs to drilling muds during the trip uphole in drilling operations. Data from coals demonstrate that these decreases in HC concentrations cannot be due to C 15 + HC thermal destruction. Oil deposits are generally found at shallow depths in basins, and “dry gas” (methane ≤ 98% of all HC gases) deposits are found at the greatest depths. This HC distribution pattern would be caused by methane, generated during the late stages of C 15 + HC generation, flushing oil (including C 2 –C 4 HC gases condensed into the liquid phase) out of deep basinal traps by Gussow's (1954) principle of differential entrapment. Hence, only “dry gas” deposits are left in the basin deeps. Oil emplacement processes in traps during expulsion and secondary migration could also contribute to the HC distribution pattern observed in petroleum basins.

Geochimica et Cosmochimica Acta↗

USGS1993

Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate

EXAFS spectra were collected on both the As and Fe K-edges from samples of two-line ferrihydrite with adsorbed (ADS) and coprecipitated (CPT) arsenate prepared over a range of conditions and arsenate surface coverages. Spectra also were collected for arsenate adsorbed on the surfaces of three FeOOH crystalline polymorphs, α (goethite), β (akaganeite), and γ (lepidocrocite), and as a free ion in aqueous: solution. Analyses of the As EXAFS show clear evidence for inner sphere bidentate (bridging) arsenate complexes on the ferrihydrite surface and on the surfaces of the crystalline FeOOH polymorphs. The bridging arsenate is attached to adjacent apices of edge-sharing Fe oxyhydroxyl octahedra. The arsenic-iron distance at the interface ( 3.28 ±0.01 A ̊ "> 3.28 ±0.01Å ) is close to that expected for this geometry on the FeOOH polymorph surfaces, but is slightly shorter on the ferrihydrite surfaces ( 3.25 ± 0.02 A ̊ "> 3.25 ± 0.02Å ). Mono-dentate arsenate linkages ( 3.60 ± 0.03 A ̊ "> 3.60 ± 0.03Å ) also occur on the ferrihydrite, but are not generally observed on the crystalline FeOOH polymorphs. The proportion of monodentate bonds appears largest for adsorption samples with the smallest As Fe "> AsFe molar ratio. In all cases the arsenate tetrahedral complex is relatively undistorted with As-O bonds of 1.66 ± 0.01 A ̊ "> 1.66 ± 0.01Å . Precipitation of arsenate or scorodite-like phases was not observed for any samples, all of which were prepared at a pH value of 8. The Fe EXAFS results confirm that the Fe-Fe correlations in the ferrihydrite are progressively disrupted in the CPT samples as the As Fe "> AsFe ratio is increased. Coherent crystallite size is probably no more than 10 Å in diameter and no Fe oxyhydroxyl octahedra corner-sharing linkages (as would be present in FeOOH polymorphs) are observed at the largest As Fe "> AsFe ratios. Comparison of the number and type of Fe-Fe neighbors with the topological constraints imposed by the arsenate saturation limit in the CPT samples (about 0.7 As Fe "> AsFe ) indicates ferrihydrite units consisting mainly of Fe oxyhydroxyl octahedra arranged in short dioctahedral chains with minimal interchain linking by octahedra corners. This is consistent with an enlarged surface area and a larger proportion of sites for bidentate arsenate bonding in CPT samples as compared to the ADS samples, which saturate with arsenate at lower As Fe "> AsFe ratios. The latter samples have larger crystallite sizes and a definite proportion of ferric octahedra sharing corners. The ratio of corner-sharing to edge-sharing Fe oxyhydroxyl octahedra in the ADS samples, and CPT samples with small As loadings, is very similar to what would be present in very small particles of goethite or akaganeite. The difference in the polymeric structure of ADS and CPT samples at higher As Fe "> AsFe ratios is due to strong arsenate bidentate adsorption that poisons the surface of particles of ferrihydrite precipitated in the presence of substantial arsenate, limiting their normal crystallization, and preventing further Fe-O-Fe polymerization. If the arsenate is applied after precipitation much less adsorption occurs since polymerization has already progressed. In both ADS and CPT samples, Fe-O-Fe polymerization increases with age, though at different rates for each type of sample.

Geochimica et Cosmochimica Acta↗

USGS1995

238U-234U-230Th chronometry of Fe-Mn crusts: Growth processes and recovery of thorium isotopic ratios of seawater

Comparison of ( ( 234 U)excess ( 238 U ) "> 234 U) excess ⁄ ( 238 U) and ( ( 230 Th 232 Th "> 230 Th ⁄ 232 Th ) activity ratios in oceanic Fe-Mn deposits provides a method for assessing the closed-system behaviour of 238 U- 234 U- 230 Th, as well as variations in the initial uranium and thorium isotopic ratios of the precipitated metal oxides. This approach is illustrated using a Fe-Mn crust from Lotab seamount (Marshall Islands, west equatorial Pacific). Here we report uranium and thorium isotopic compositions in five subsamples from the surface of one large 5 cm diameter botryoid of this crust, and from two depth profiles of the outermost rim of the same botryoid. The decrease of ( ( 234 U)excess ( 238 U ) "> 234 U) excess ⁄ ( 238 U) and ( ( 230 Th 232 Th "> 230 Th ⁄ 232 Th ) activity ratio with depth in the two profiles gives mean growth rates, for the last 150 ka, of 7.8 ± 2 mm/Ma and 6.6 ± 1 mm/Ma, respectively. All data points (surface and core samples) but one, define a linear correlation in the Ln ( 230 Th 232 Th − Ln ( 234 U)excess ( 238 U ) "> Ln ( ( 230 Th 232 Th "> 230 Th ⁄ 232 Th ) −Ln[ ( ( 234 U)excess ( 238 U ) "> 234 U) excess ⁄ ( 238 U) ] diagram. This correlation indicates that for all points the U-Th system remained closed after the Fe-Mn layer precipitated, and that the different samples possessed the same initial Uranium and thorium isotope ratios. Furthermore, these results show that the preserved surface of this Fe-Mn crust may not be the present-day growth surface, and that the thorium and uranium isotopic ratios of seawater in west equatorial Pacific have not changed during the past 150 ka. The initial thorium activity ratio is estimated from the correlation obtained between Ln ( 230 Th 232 Th − Ln ( 234 U)excess ( 238 U ) "> Ln ( ( 230 Th 232 Th "> 230 Th ⁄ 232 Th ) −Ln Ln ( 230 Th 232 Th − Ln ( 234 U)excess ( 238 U ) ">[ ( ( 234 U)excess ( 238 U ) "> 234 U) excess ⁄ ( 238 U) ] .

Lotab Seamount, Pacific Ocean↗

USGS1994

Zinc, copper, and lead in mid-ocean ridge basalts and the source rock control on Zn/Pb in ocean-ridge hydrothermal deposits

The contents of Zn, Cu, and Pb in mid-ocean ridge basalts (MORB) and the MORB source-rock control on Zn/Pb in ocean-ridge hydrothermal deposits are examined. The values of Zn, Cu, and Pb for submarine mid-ocean ridge basalts (MORB) are, respectively (in ppm): average MORB—75, 75, and 0.7; West Valley, Juan de Fuca Ridge (JFR)—87, 64, and 0.5; southern JFR—120 and 0.5; and 21°N, East Pacific Rise (EPR)—73, 78, and 0.5. Values of Zn/Pb range from about 100–240 and Cu/ Pb from 100–156. In this study, Zn is found to correlate positively with TiO 2 + FeO (mean square of weighted deviates, MSWD, of 1.6 for JFR basalt), and inversely with Mg number (MSWD of 3.5). Therefore, contrary to statements in the literature that Zn should be compatible in MORB, Zn is a mildly incompatible element and must be enriched in the glass phase relative to olivine as Zn does not fit into the other major phenocryst phase, plagioclase. In the source of MORB, Zn likely is most enriched in oxides: spinel, magnetite, and titanomagnetite. Copper generally does not correlate well with other elements in most MORB data examined. When differentiation is dominated by olivine, Cu has a tendency to behave incompatibly (e.g., at Mg numbers > 70), but, overall, Cu shows some tendency towards being a compatible element, particularly along the Mid-Atlantic Ridge, a behavior presumably due to separation of sulfides in which Cu (but not Zn) is markedly enriched. Copper thus may be in dispersed sulfides in the source of MORB. Ocean ridges provide important data on source-rock controls for sulfide deposits because, in sediment-starved ridges, much is known about the possible source rocks and mineralization is presently occurring. In contrast to Zn/Pb ~5 in continental hot Cl-rich brines, Zn/Pb in the hottest sediment-starved ridge black smoker hydrothermal fluids at 21 °N, EPR is about 110, similar to local MORB (145), but Cu/Pb is closer to 30, possibly due to subsurface deposition of Cu. At the JFR, the best value of Zn/Pb in the hydrothermal fluids is about 175, again similar to local MORB (240), but Cu is very low in the fluids that are at temperatures less than 300°C. The large MORB-like Zn/Pb in the hottest black-smoker fluids suggests a source-rock control for the metals that prohibits significant galena in the black-smoker deposits of sediment-starved ridges. In contrast, exhalative deposits on sediment-swamped ridges have significant galena; its presence is suggestive of Pb derivation from sediments, an origin supported by Pb isotope studies of LeHuray and colleagues in 1988.

Geochimica et Cosmochimica Acta↗

USGS1994

Hydrothermal alteration in oceanic ridge volcanics: A detailed study at the Galapagos Fossil Hydrothermal Field

The Galapagos Fossil Hydrothermal Field is composed of altered oceanic crust and extinct hydrothermal vents within the eastern Galapagos Rift between 85°49′W and 85°55′W. The discharge zone of the hydrothermal system is revealed along scarps, thus providing an opportunity to examine the uppermost mineralized, and highly altered interior parts of the crust. Altered rocks collected in situ by the submersible ALVIN show complex concentric alteration zones. Microsamples of individual zones have been analysed for major/minor, trace elements, and strontium isotopes in order to describe the complex compositional details of the hydrothermal alteration. Interlayered chlorite-smectite and chlorite with disequilibrium compositions dominate the secondary mineralogy as replacement phases of primary glass and acicular pyroxene. Phenocrysts and matrix grains of plagioclase are unaffected during alteration. Using a modification of the Gresens' equation we demonstrate that the trivalent rare earth elements (REEs) are relatively immobile, and calculate degrees of enrichment and depletion in other elements. Strontium isotopic ratios increase as Sr concentrations decrease from least-altered cores to most-altered rims and cross-cutting veins in individual samples, and can be modeled by open system behaviour under low fluid-rock ratio (< 10) conditions following a period of lower-temperature weathering of volcanics within the rift zone. The complex patterns of element enrichment and depletion and strontium isotope variations indicate mixing between pristine seawater and ascending hot fluids to produce a compositional spectrum of fluids. The precipitation of base-metal sulfides beneath the seafloor is probably a result of fluid mixing and cooling. If, as suggested here, the discharge zone alteration occurred under relatively low fluid-rock ratios, then this shallow region must play an important role in determining the exit composition of vent fluids in marine hydrothermal systems.

Geochimica et Cosmochimica Acta↗

USGS1994

A precise 232Th-208Pb chronology of fine-grained monazite: Age of the Bayan Obo REE-Fe-Nb ore deposit, China

We have obtained precise Th-Pb internal isochron ages on monazite and bastnaesite for the world's largest known rare earth elements (REE)-Fe-Nb ore deposit, the Bayan Obo of Inner Mongolia, China. The monazite samples, collected from the carbonate-hosted ore zone, contain extremely small amounts of uranium (less than 10 ppm) but up to 0.7% ThO 2 . Previous estimates of the age of mineralization ranged from 1.8 to 0.255 Ga. Magnetic fractions of monazite and bastnaesite samples (<60-μm size) showed large ranges in 232 Th 204 Pb "> 232 Th 204 Pb values (900–400,000) and provided precise Th-Pb internal isochron ages for paragenetic monazite mineralization ranging from 555 to 398 Ma within a few percent error (0.8% for two samples). These results are the first indication that REE mineralization within the giant Bayan Obo ore deposit occurred over a long period of time. The initial lead isotopic compositions (low 206 Pb 204 Pb "> 206 Pb 204 Pb and high 208 Pb 204 Pb) "> 208 Pb 204 Pb) and large negative ϵ Nd values for Bayan Obo ore minerals indicate that the main source(s) for the ores was the lower crust which was depleted in uranium, but enriched in thorium and light rare earth elements for a long period of time. Zircon from a quartz monzonite, located 50 km south of the ore complex and thought to be related to Caledonian subduction, gave an age of 451 Ma, within the range of monazite ages. Textural relations together with the mineral ages favor an epigenetic rather than a syngenetic origin for the orebodies. REE mineralization started around 555 Ma (disseminated monazite in the West, the Main, and south of the East Orebody), but the main mineralization (banded ores) was related to the Caledonian subduction event ca. 474-400 Ma.

Bayan Obo, Kuanggou Fault↗

USGS1994

Composition and sources of atmospheric dusts in snow at 3200 meters in the St. Elias Range, southeastern Alaska, USA

Dusts in snow from the accumulation zone in the St. Elias Range appear from their chemical compositions to have come from terranes of rocks of ferromagnesian composition. These dusts, with respect to their composition and to the moderate degree of variation that occurs through a depositional year, are similar those deposited in Greenland. The high portion of the St. Elias Range is isolated from dominance by any local dust source terranes, because of altitude and the extent of the surrounding glacierized and snow-covered region. In Greenland the altitude is typically lower, but local sources are even less likely to dominate the character of the dusts deposited into the ice record there. The similar compositions and moderate compositional variations of dusts from these two places bear on the question of whether the dusts that are transported over long distances by the atmosphere under modern and glacial-period conditions are uniform and representative of a broad regional or even hemispheric background dust. The dusts in the snow were measured by means of a suite of major, minor, and trace rock-forming metals chosen to give information about rock types, their constituent minerals, degree of degradation (weathering), and energies of atmospheric uptake from source. The variations in amounts of rock dust through the year in the St. Elias Range snowpack have no time-stratigraphic correspondence to the also large variations in concentrations of other species that are not constituents of rock-derived dusts, such the anions chloride, sulfate, and nitrate; the highs and lows of the two types of materials are apparently completely independent. The structure revealed by the moderately fine-scale sampling of the present study (≈ 10 increments/y) serves as a background for the interpretation of analysis of ice core samples, in which annual layers may be too compressed to permit analysis of sub-annual samples.

Alaska↗

USGS1994

Fractionation of families of major, minor, and trace metals across the melt-vapor interface in volcanic exhalations

Chemical families of metals fractionate systematically as they pass from a silicate melt across the interface with the vapor phase and on into a cooled volcanic plume. We measured three groups of metals in a small suite of samples collected on filters from the plumes of Kilauea (Hawaii, USA), Etna (Sicily), and Merapi (Java) volcanoes. These were the major, minor, and trace metals of the alkali and alkaline earth families (K, Rb, Cs, Ca, Sr, Ba), a group of ordinarily rare metals (Cd, Cu, In, Pb, Tl) that are related by their chalcophile affinities, and the radon daughter nuclides 210Po, 210Bi, and 210Pb. The measurements show the range and some details of systematic melt-vapor fractionation within and between these groups of metals. In the plumes of all three volcanoes, the alkali metals are much more abundant than the alkaline earth metals. In the Kilauea plume, the alkali metals are at least six times more abundant than the alkaline earth metals, relative to abundances in the melt; at Etna, the factor is at least 300. Fractionations within each family are, commonly, also distinctive; in the Kilauea plume, in addition to the whole alkaline earth family being depleted, the heaviest metals of the family (Sr, Ba) are progressively more depleted than the light metal Ca. In plumes of fumaroles at Merapi, K/Cs ratios were approximately three orders of magnitude smaller than found in other earth materials. This may represent the largest observed enrichment of the "light ion lithophile" (LIL) metals. Changes in metal ratios were seen through the time of eruption in the plumes of Kilauea and Etna. This may reflect degree of degassing of volatiles, with which metals complex, from the magma bodies. At Kilauea, the changes in fractionation were seen over about three years; fractionation within the alkaline earth family increased, and that between the two families decreased, over that time. All of the ordinarily rare chalcophile metals measured are extremely abundant in volcanic plumes, and Cd and Tl are enriched relative to the others. Indium is much more abundant in the plume of the hotspot volcano Kilauea than in the Etna plume (probably non-hotspot in character). It may be a useful indicator of the tapping of deep mantle zones, or could aid in the interpretation of reports of Pt group metals in exhalations from hot spot volcanoes. Indium in old glacial ice strata could help assess magnitude and variability of exhalations from hotspot volcanoes in past time. Strong melt-vapor fractionation of the alkali and alkaline earth metals may only be observed in plumes during quiescent degassing of volcanoes; when large amounts of ash or spatter (undifferentiated lava) enter the plume, its alkali and alkaline earth metal composition may approach that of the melt. Ratios among the chalcophile metals may not be much changed by addition of ash, because their concentrations in melt are so small, and masses of them in any plume may remain dominated by transfer across the melt-vapor interface. Radon daughter nuclides give information about state of volcanic activity at time of sampling. The precisely known origins, ultratrace detectability, decay systematics, and wide variations in volatility of these species provide information about residence times, degassing and travel histories, and identities of melt bodies in volcanic systems. ?? 1994.

Geochimica et Cosmochimica Acta↗

USGS1994

Geochemistry and hydrology of a calcareous fen within the Savage Fen wetlands complex, Minnesota, USA

Savage Fen is a wetlands complex at the base of north-facing bluffs in the Minnesota River Valley. The complex includes 27.8 hectares of calcareous fen that host rare calciphile plants whose populations are declining in Minnesota. Water and sediment compositions in the calcareous fen were studied to gain a better understanding of the hydrologie System that sustains the rare vegetation. Groundwater in the fen is a calcium-magnesium-bicarbonate type with circumneutral pH values. The groundwater composition is the resuit of interactions among water, dissolved and gaseous carbon species, carbonates, and ion exchangers. Shallow groundwater is distinguished from deep groundwater by smaller concentrations of chloride, sulfate, magnesium, and sodium, and larger concentrations of calcium, bicarbonate, hydrogen sulfide, and ammonium. Magnesian calcite is the prevalent carbonate in unconsolidated sedimentary fill beneath the fen and is an important source and sink for dissolved calcium, magnesium, and inorganic carbon. Calcite concentrations just below the water table are small because aerobic and anaerobic oxidation of organic matter increase the partial pressure of carbon dioxide ( P CO 2 ), decrease pH, and cause calcite to dissolve. Thick calcite accumulations just above the water table, in the root zone of calciphile plants, result from water table fluctuations and attendant changes in P CO 2 . Groundwater beneath Savage Fen recharges in lakes and ponds south of the fen and upwells to the surface within the fen. Water at the water table is a mixture of upwelling groundwater and water near the surface that flows downslope from higher elevations in the fen. Changes in oxygen and hydrogen isotope compositions of shallow groundwater indicate that the proportion of upwelling groundwater in shallow groundwater decreases downgradient in the calcareous fen. Encroachment of reed grasses into the calcareous fen may reflect human-caused disturbances in the recharge area.

Minnesota↗

USGS1994

Surface alteration and physical properties of glass from the Cretaceous-Tertiary boundary

The scalloped surface feature on Cretaceous-Tertiary boundary glass is often explained as being due to terrestrial aqueous leaching. Leaching of man-made glass results in a reduction in density of the glass. Also, Fe, because of its relative insolubility, is concentrated by the leaching process. Thus, the Haitian glass specimens which have been heavily altered should have a thin rim of less dense glass in which the Fe is concentrated compared to the core glass. The higher Fe concentration in the rim glass should cause it to have an enhanced Curie constant and a lower density compared to the unaltered glass. The magnetic Curie constant, density, and scanning electron microscopic studies were made on altered specimens of Haitian glass and also on specimens showing a minimum of alteration. The results show that the less altered samples have the highest density and the lowest Curie constant. The data substantiate the terrestrial hypothesis.

Geochimica et Cosmochimica Acta↗

USGS1994

Clastic metasediments of the Early Proterozoic Broken Hill Group, New South Wales, Australia: Geochemistry, provenance, and metallogenic significance

Whole-rock analyses of samples of pelite, psammite, and psammopelite from the Early Proterozoic Broken Hill Group (Willyama Supergroup) in the Broken Hill Block, New South Wales, Australia, reveal distinctive geochemical signatures. Major-element data show high Al 2 O 3 and K 2 O, low MgO and Na 2 O, and relatively high Fe 2 O 3 T MgO "> Fe2O3TMgO ratios, compared to average Early Proterozoic clastic metasediments. High field strength elements (HFSE) are especially abundant, including Nb (most 15–27 ppm), Ta (most 1.0–2.2 ppm), Th (17–36 ppm), Hf (4–15 ppm), and Zr (most 170–400 ppm); Y (33–74 ppm) is also high. Concentrations of ferromagnesian elements are generally low ( Sc = < 20 ppm, Ni = ≤ 62 ppm, Co = <26 ppm; Cr = most < 100 ppm). Data for rare earth elements (REEs) show high abundances of light REEs ( La CN = 116–250 × chondrite; La CN = 437 in one sample), high La CN Yb CN "> LaCNYbCN ratios (5.6–13.9), and large negative Eu anomalies ( Eu Eu ∗ = 0.32–0.57 "> EuEu∗= 0.32–0.57 ). The geochemical data indicate derivation of the metasedimentary rocks of the Broken Hill Group by the erosion mainly of felsic igneous (or meta-igneous) rocks. High concentrations of HFSE, Y, and REEs in the metasediments suggest a provenance dominanted by anorogenic granites and(or) rhyolites, including those with A-type chemistry. Likely sources of the metasediments were the rhyolitic to rhyodacitic protoliths of local quartz + feldspar ± biotite ± garnet gneisses (e.g., Potosi-type gneiss) that occur within the lower part of the Willyama Supergroup, or chemically similar basement rocks in the region; alternative sources may have included Early Proterozoic anorogenic granites and(or) rhyolites in the Mount Isa and(or) Pine Creek Blocks of northern Australia, or in the Gawler craton of South Australia. Metallogenic considerations suggest that the metasediments of the Broken Hill Block formed enriched source rocks during the generation of pegmatite-hosted deposits and concentrations of La, Ce, Nb, Ta, Th, and Sn in the region. Li, Be, B, W, and U in pegmatite minerals of the district may have been acquired during granulite-facies metamorphism of the local metasediments.

New South Wales↗

USGS1994

An experimental study of zinc chloride speciation from 300 to 600 °C and 0.5 to 2.0 kbar in buffered hydrothermal solutions

The solubility of sphalerite (ZnS) was measured in KCl-HCl-H 2 O solutions at 300–600°C and 0.5–2.0 kbar. The silicate assemblage K-feldspar-muscovite (or andalusite)-quartz was used to buffer the solution to acid conditions, resulting in the total solubility reaction 2 K + + KAl 2 AlSi 3 O 10 ( OH ) 2 + 6 SiO 2 + ZnS + nCl − = ZnCl n (2− n ) + 3 KAlSi 3 O 8 + H 2 S . (muscovite) (quartz) (sphalerite) (K-feldspar) A computer retrieval technique was used to derive average chloride ligand numbers for chlorozinc species at 0.25–2.0 molal total chloride. This technique mathematically solves for the average ligand number using a series of pertinent chemical relations at P and T . Mono- and di-chlorozinc species were found to predominate throughout the pressure-temperature-composition range investigated. The logarithms of the first and second dissociation constants for ZnCl 2 0 were evaluated over the P - T range; for example, at 1 kbar, the values −0.41 and −1.42 were computed for the logarithm of the first dissociation constant, while −7.62 and −10.57 were computed for the logarithm of the second dissociation constant, for 400 and 500°C, respectively. Results are compared to past studies conducted at subcritical conditions and differ in that we find no evidence for more highly coordinated chloro-zinc species except possibly for ZnCl 3 − at 600°C, 1 and 2 kbar. Our results are consistent with electrostatic theory, which favors lower charged to neutral molecules in low dielectric-constant media.

Geochimica et Cosmochimica Acta↗

USGS1994

Mobilization of beryllium in the sedimentary column at convergent margins

Studies of Be distributions in subduction zone sediments will help to understand questions regarding the enrichments of cosmogenic Be-10 in arc volcanic rocks. Analyses of Be-10 and Be-9 in sediments of Ocean Drilling Program Site 808, Nankai Trough and Be-9 in porewaters of Site 808 and Sites 671 and 672, Barbados ridge complex, show significant decreases in solid phase Be-10 and large increases of porewater Be-9 at the location of the décollement zone and below or at potential flow conduits. These data imply the potential mobilization of Be during pore fluid expulsion upon sediment burial. Experiments involving reaction between a décollement sediment and a synthetic NaCl-CaCl 2 solution at elevated pressure and temperatures were conducted in an attempt to mimic early subduction zone processes. The results demonstrate that Be is mobilized under elevated pressure and temperature with a strong pH dependence. The Be mobilization provides an explanation of Be-10 enrichment in arc volcanic rocks and supports the argument of the importance of the fluid processes in subduction zones at convergent margins.

Nankai Trough, Pacific Ocean↗

USGS1994

Calculation of 230ThU isochrons, ages, and errors

If analytical errors are responsible for the scatter of points on a 230 Th- 234 U- 238 U isochron diagram, the isochron should be fitted by a technique that 1. weights the points according to their analytical errors and error correlations, and 2. either takes into account the presence of some of the same data in two coupled XY isochrons or (equivalently) uses a single, three-dimensional XYZ isochron. A method based on maximum-likelihood estimation is presented that fulfills these requirements, and the relevant equations for errors in age and initial 234 U 238 U "> 234 U 238 U are given. Equations for estimating the necessary isotope-ratio errors and error-correlations for both alpha-spectrometric and mass-spectrometric data are also developed.

Geochimica et Cosmochimica Acta↗

USGS1994

Variations in the chemical and stable isotope composition of carbon and sulfur species during organic-rich sediment alteration: An experimental and theoretical study of hydrothermal activity at Guaymas Basin, Gulf of California

Organic-rich diatomaceous ooze was reacted with seawater and a Na-Ca-K-Cl fluid of seawater chlorinity at 325–400°C, 400–500 bars, and fluid/sediment mass ratios of 1.56–2.35 to constrain factors regulating the abundance and stable isotope composition of C and S species during hydrothermal alteration of sediment from Guaymas Basin, Gulf of California. Alteration of inorganic and organic sedimentary components resulted in extensive exchange reactions, the release of abundant H 2 S, CO 2 , CH 4 , and C organic , to solution, and recrystallization of the sediment to an assemblage containing albitic plagioclase, quartz, pyrrhotite, and calcite. The δ 34 S cdt "> δ 34 S cdt values of dissolved H 2 S varied from −10.9 to +4.3‰ during seawater-sediment interaction at 325 and 400°C and from −16.5 to −9.0‰ during Na-Ca-K-Cl fluid-sediment interaction at 325 and 375°C. In the absence of seawater SO 4 , H 2 S is derived from both the transformation of pyrite to pyrrhotite and S released during the degradation of organic matter. In the presence of seawater SO 4 , reduction of SO 4 contributes directly to H 2 S production. Sedimentary organic matter acts as the reducing agent during pyrite and SO 4 reduction. Requisite acidity for the reduction of SO 4 is provided by Mg fixation during early-stage sediment alteration and by albite and calcite formation in Mg-free solutions. Organically derived CH 4 was characterized by δ 13 C pdb "> δ13Cpdb values ranging between −20.8 and −23.1‰, whereas δ 13 C pdb "> δ 13 C pdb values for dissolved C organic ranged between −14.8 and −17.7%. Mass balance calculations indicate that δ 13 C values for organically derived CO 2 were ≥ − 14.8%. Residual solid sedimentary organic C showed small (≤ 0.7‰) depletions in 13 C relative to the starting sediment. The experimental results are consistent with the isotopic and chemical composition of natural hydrothermal fluids and minerals at Guaymas Basin and permit us to better constrain sources and sinks for C and S species in subseafloor hydrothermal systems at sediment-covered spreading centers. Our data show that the sulfur isotope composition of hydrothermal Sulfide minerals in Guaymas Basin can be explained by derivation of S from diagenetic sulfide and seawater sulfate. Basaltic S may also contribute to hydrothermal sulfide precipitates but is not required to explain their isotopic composition. Estimates of seawater/ sediment mass ratios based on sulfur isotopic composition of sulfide minerals and the abundance of dissolved NH 3 in vent fluids range from 3–29 during hydrothermal circulation. Sources of C in Guaymas Basin hydrothermal fluids include thermal degradation of organic matter, bacteriogenic methane production, and dissolution of diagenetic carbonate.

Baja California Sur↗

USGS1994

Uranium(VI) adsorption to ferrihydrite: Application of a surface complexation model

A study of U(VI) adsorption by ferrihydrite was conducted over a wide range of U(VI) concentrations, pH, and at two partial pressures of carbon dioxide. A two-site (strong- and weak-affinity sites, Fe s OH and Fe w OH, respectively) surface complexation model was able to describe the experimental data well over a wide range of conditions, with only one species formed with each site type: an inner-sphere, mononuclear, bidentate complex of the type (FeO 2 )UO 2 . The existence of such a surface species was supported by results of uranium EXAFS spectroscopy performed on two samples with U(VI) adsorption density in the upper range observed in this study (10 and 18% occupancy of total surface sites). Adsorption data in the alkaline pH range suggested the existence of a second surface species, modeled as a ternary surface complex with UO 2 CO 3 0 binding to a bidentate surface site. Previous surface complexation models for U(VI) adsorption have proposed surface species that are identical to the predominant aqueous species, e.g., multinuclear hydrolysis complexes or several U(VI)-carbonate complexes. The results demonstrate that the speciation of adsorbed U(VI) may be constrained by the coordination environment at the surface, giving rise to surface speciation for U(VI) that is significantly less complex than aqueous speciation.

Geochimica et Cosmochimica Acta↗

USGS1994

The geochemical cycling of trace elements in a biogenic meromictic lake

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d-1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn).

Geochimica et Cosmochimica Acta↗