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Coprecipitation mechanisms and products in manganese oxidation in the presence of cadmium

Manganese oxidation products were precipitated in an aerated open-aqueous system where a continuous influx of mixed Mn 2+ and Cd 2+ solution was supplied and pH was maintained with an automated pH-stat adding dilute NaOH. X-ray diffraction and electron diffraction identified the solids produced as mixtures of Cd 2 Mn 3 4+ O 8 , Mn 2+ 2 Mn 4+ 3 O 8 , MnO 2 (ramsdellite), and CdCO 3 . Mean oxidation numbers of the total precipitated Mn as great as 3.6 were reached during titrations. During subsequent aging in solution, oxidation numbers between 3.8 and 3.9 were reached in some precipitates in less than 40 days. Conditional oxidation rate constants calculated from a crystal-growth equation applied to titration data showed the overall precipitation rate, without considering manganese oxidation state in the precipitate, was increased by a factor of ~4 to ~7 when the mole ratio (Cd/Mn + Cd) of cadmium in the feed solution was 0.40 compared with rate constants for hausmannite (Mn 2+ Mn 2 3+ O 4 precipitation under similar conditions but without accessory metals. Kinetic experiments were made to test effects of various Cd/Mn + Cd mole ratios and rates of addition of the feed solution, different temperatures from 5.0 to 35°C, and pH from 8.0 to 9.0. Oxidation rates were slower when the Cd mole ratio was less than 0.40. The rate increased by a factor of ~10 when pH was raised one-half unit. The effect of temperature on the rate constants was also substantial, but the meaning of this is uncertain because the rate of formation of Mn 4+ oxide in the absence of Cd or other accessory metals was too slow to be measurable in titration experiments. The increased rate of Mn 4+ oxide formation in the presence of Cd 2+ can be ascribed to the formation of a labile adsorbed intermediate, CdMn 2 O 4 Int , an analog of hausmannite, formed on precipitate surfaces at the beginning of the oxidation process. The increased lability of this structure, resulting from coordination-chemical behavior of Cd 2+ during the titration, causes a rapid second-stage rearrangement and facilitates disproportionation of the Mn 3+ ions. The Mn 2+ ions thus released provide a positive feedback mechanism that couples the two steps of the conversion of Mn 2+ to Mn 4+ more closely than is possible when other metal ions besides manganese are not present. During aging of precipitates in contact with solutions, proportions of Cd 2 Mn 3 O 8 and MnO 2 increased at the expense of other precipitate components.

Geochimica et Cosmochimica Acta↗

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↗

Effects of karst and geologic structure on the circulation of water and permeability in carbonate aquifers

The results of the natural processes caused by solution and leaching of limestone, dolomite, gypsum, salt and other soluble rocks, is known as karst. Development of karst is commonly known as karstification, which may have a pronounced effect on the topography, hydrology and environment, especially where such karst features as sinkholes and vertical solution shafts extend below the land surface and intersect lateral solution passages, cavities, caverns and other karst features in carbonate rocks. Karst features may be divided into two groups: (1) surficial features that do not extend far below the surface; and (2) karst features such as sinkholes that extend below the surface and affect the circulation of water below. The permeability of the most productive carbonate aquifers is due chiefly to enlargement of fractures and other openings by circulation of water. Important controlling factors responsible for the development of karst and permeability in carbonate aquifers include: (1) climate, topography, and presence of soluble rocks; (2) geologic structure; (3) nature of underground circulation; and (4) base level. Another important factor is the condition of the surface of the carbonate rocks at the time they are exposed to meteoric water. A carbonate rock surface, with soil or relatively permeable, less soluble cover, is more favorable for initiation of karstification and solution than bare rocks. Water percolates downward through the cover to the underlying carbonate rocks instead of running off on the surface. Also, the water becomes more corrosive as it percolates through the permeable cover to the underlying carbonate rocks. Where there is no cover or the cover has been removed, the carbonate rocks become case hardened and resistant to erosion. However, in regions underlain not only by carbonate rocks but also by beds of anhydrite, gypsum and salt, such as the Hueco Plateau in southeastern New Mexico, subsurface solution may occur where water without natural acids moves down from bare rock surfaces through cracks to the beds that are more soluble than carbonate rocks. For example, in the area of Carlsbad Caverns in southeastern New Mexico, much of the water responsible for solution that formed the caverns apparently entered the groundwater system through large open fractures and did not form sinkhole topography. East of the Carlsbad Caverns, however, in the Pecos River Valley where the carbonate rocks are overlain by the less soluble Ogallala Formation of Late Tertiary age, solution began along escarpments as the Pecos River and its tributaries cut through the less soluble cover. As these escarpments retreated, sinkholes and other karst features developed. Joints or fractures are essential for initiation of downward percolation of water in compact carbonate rocks such as some Paleozoic limestone in which there is no intergranular permeability. Also joints or fractures and bedding planes may be essential in the initiation of lateral movement of water in the zone of saturation. Where conditions of recharge and discharge are favorable, groundwater may move parallel to the dip. However, the direction of movement of water in most carbonate rocks is not necessarily down dip or parallel to the dip. The general direction of movement of both surface and groundwater may be parallel to the strike in a breached anticline. Faults may restrict the lateral movement of water, especially if water-bearing beds are faulted against relatively impervious beds. Conversely, some fault may serve as avenues through which water may move as, for example, in the Cretaceous Edwards aquifer in the San Antonio area, Texas. Karst aquifers, chiefly carbonate rocks, may be placed in three groups according to water-bearing capacity. Water in aquifers of group 1 occurs chiefly in joints, fractures, and other openings that have not been enlarged by solution. The yield of wells is small. Aquifers in group 2 , with low to intermediate yields, are those in which water occurs in joints and fractures with some cavities and channels enlarged by solution. Aquifers in group 3 are those in which the yield of wells and springs range from intermediate to very large. This group includes five of the most productive aquifers in the U.S.A. The water-bearing beds of all of these productive aquifers, except the Biscayne aquifer in southeastern Florida, contain buried paleokarst in which the permeability has been reactivated and enlarged by the present circulation system.

Journal of Hydrology↗

Seasonal cycles of dissolved constituents in streamwater in two forested catchments in the mid-Atlantic region of the eastern U.S.A.

Streamwater discharge and chemistry of two small catchments on Catoctin Mountain in north-central Maryland have been monitored since 1982. Repetitive seasonal cycles in stream-water chemistry have been observed each year, along with seasonal cycles in the volume of stream discharge and in groundwater levels. The hypothesis that the observed streamwater chemical cycles are related to seasonal changes in the hydrological flow paths that contribute to streamflow is examined using a combination of data on groundwater levels, shallow and deep groundwater chemistry, streamwater discharge, streamwater chemistry, soil-water chemistry, and estimates of water residence times. The concentrations of constituents derived from rock weathering, particularly bicarbonate and silica, increase in streamwater during the summer when the water table is below the regolith-bedrock interface and stream discharge consists primarily of deep groundwater from the fractured-bedrock aquifer. Conversely, the concentrations in streamwater of atmospherically derived components, particularly sulfate, increase in winter when the water table is above the regolith-bedrock interface and stream discharge consists primarily of shallow groundwater from the regolith. Tritium and chlorofluorocarbon (CFC) measurements suggest that the groundwater in these systems is young, with a residence time of less than several years. The results of this study have implications for the design of large-scale water-quality monitoring programs.

Maryland↗

Wave-formed structures and paleoenvironmental reconstruction

Wave-formed sedimentary structures can be powerful interpretive tools because they reflect not only the velocity and direction of the oscillatory currents, but also the length of the horizontal component of orbital motion and the presence of velocity asymmetry within the flow. Several of these aspects can be related through standard wave theories to combinations of wave dimensions and water depth that have definable natural limits. For a particular grain size, threshold of particle movement and that of conversion from a rippled to flat bed indicate flow-velocity limits. The ratio of ripple spacing to grain size provides an estimate of the length of the near-bottom orbital motion. The degree of velocity asymmetry is related to the asymmetry of the bedforms, though it presently cannot be estimated with confidence. A plot of water depth versus wave height (h-H diagram) provides a convenient approach for showing the combination of wave parameters and water depths capable of generating any particular structure in sand of a given grain size. Natural limits on wave height and inferences or assumptions regarding either water depth or wave period based on geologic evidence allow refinement of the paleoenvironmental reconstruction. The assumptions and the degree of approximation involved in the different techniques impose significant constraints. Inferences based on wave-formed structures are most reliable when they are drawn in the context of other evidence such as the association of sedimentary features or progradational sequences.

Marine Geology↗

The potential of paleozoic nonmarine trace fossils for paleoecological interpretations

Many Late Paleozoic environments have been interpreted as marine because of the co-occurrence of supposedly exclusively marine trace fossils. Beginning in the Late Ordovician, however, nonmarine trace-fossil diversity increased throughout the Paleozoic. This diversification of nonmarine organisms and nonmarine trace fossils was especially prevalent in Devonian and later times. Diversification of freshwater organisms is indicated by the large number of freshwater fish, arthropods, annelids and molluscs that had developed by the Carboniferous. In addition to diverse freshwater assemblages, entirely terrestrial vertebrate and invertebrate ecosystems had developed by the Devonian. This rapid diversification of freshwater and terrestrial organisms is inherently linked to development and diversification of land plants and subsequent shedding of large quantities of organic detritus in nonmarine and marginal-marine areas. Nearshore marine organisms and their larvae that are able to tolerate relatively short periods of lowered salinities will follow salt-water wedges inland during times of reduced freshwater discharge. Similarly, amphidromous marine organisms will migrate periodically inland into nonmarine environments. Undoubtedly, both of these processes were active in the Paleozoic. However, both processes are restricted to stream/distributary channels, interdistributary bays, or estuaries. Therefore, the presence of diverse trace-fossil assemblages in association with floodplain deposits is interpreted to reflect true nonmarine adaptation and diversity. Conversely, diverse trace-fossil assemblages in association with stream/distributary channel deposits, interdistributary-bay deposits, or estuarine deposits may reflect migration of salt-water wedges inland, or migration of marine organisms into freshwater environments (amphidromy), or both.

Palaeogeography, Palaeoclimatology, Palaeoecology↗

Remote sensing data of SP Mountain and SP Lava flow in north-central Arizona

Multifrequency airborne radar image data of SP Mountain [Official name of feature (U.S. Geological Survey, 1970)] and SP flow (and vicinity) in north-central Arizona were obtained in diverse viewing directions and direct and cross-polarization, then compared with surface and aerial photography, LANDSAT multispectral scanner data, airborne thermal infrared imagery, surface geology, and surface roughness statistics. The extremely blocky, basaltic andesite of SP flow is significantly brighter on direct-polarization K-band (0.9-cm wavelength) images than on cross-polarized images taken simultaneously. Conversely, for the longer wavelength (25 cm) L-band radar images, the cross-polarization image returns from SP flow are brighter than the direct-polarized image. This effect is explained by multiple scattering and the strong wavelength dependence of polarization effects caused by the rectilinear basaltic andesite scatters. Two distinct types of surface relief on SP flow, one extremely blocky, the other subdued, are found to be clearly discriminated on the visible and thermal wavelength images but are separable only on the longer wavelength L-band radar image data. The inability of the K- and X- (3-cm wavelength) band radars to portray the differences in roughness between the two SP flow surface units is attributed to the radar frequency dependence of the surface-relief scale, which, described as the Rayleigh criterion, represents the transition between quasispecular and primarily diffuse backscatter.

Arizona↗

Separation of arsenic(III) and arsenic(V) in ground waters by ion-exchange

The predominant species of arsenic in ground water are probably arsenite and arsenate. These can be separated with a strong anion-exchange resin (Dowex 1 × 8; 100–200 mesh, acetate form) in a 10 cm × 7 mm column. Samples are filtered and acidified with concentrated hydrochloric acid (1 ml per 100 ml of sample) at the sample site. Five ml of the acidified sample are used for the separation. At this acidity, As(III) passes through the acetate-form resin, and As(V) is retained. As(V) is eluted by passage of 0.12 M hydrochloric acid through the column (resulting in conversion of the resin back into the chloride form). Samples are collected in 5-ml portions up to a total of 20 ml. The arsenic concentration in each portion is determined by graphite-furnace atomic-absorption spectrophotometry. The first two fractions give the As(III) concentration and the last two the As(V) concentration. The detection limit for the concentration of each species is 1 μg l "> μ gl.

Talanta↗

Thin and layered subcontinental crust of the Great Basin western North America inherited from Paleozoic marginal ocean basins?

The seismic profile of the crust of the northern part of the Basin and Range province by its thinness and layering is intermediate between typical continental and oceanic crust and resembles that of marginal ocean basins, especially those with thick sedimentary fill. The geologic history of the Great Basin indicates that it was the site of a succession of marginal ocean basins opening and closing behind volcanic arcs during much of Paleozoic time. A long process of sedimentation and deformation followed throughout the Mesozoic modifying, but possibly not completely transforming the originally oceanic crust to continental crust. In the Cenozoic, after at least 40 m.y. of quiescence and stable conditions, substantial crustal and upper-mantle changes are recorded by elevation of the entire region in isostatic equilibrium, crustal extension resulting in Basin and Range faulting, extensive volcanism, high heat flow and a low-velocity mantle. These phenomena, apparently the result of plate tectonics, are superimposed on the inherited subcontinental crust that developed from an oceanic origin in Paleozoic time and possibly retained some of its thin and layered characteristics. The present anomalous crust in the Great Basin represents an accretion of oceanic geosynclinal material to a Precambrian continental nucleus apparently as an intermediate step in the process of conversion of oceanic crust into a stable continental landmass or craton.

western North America↗

Inbreeding in fish populations used for aquaculture

The theoretical causes of inbreeding depression are reviewed. Studies to measure depression at a series of inbreeding levels in rainbow trout populations using the method of inbred-outbred half-sib families are discussed. While the actual depression estimates varied widely between populations and inbreeding levels, significant levels of depression were found in many hatchery, field, and brood stock performance traits after only one generation of brother-sister mating. Especially susceptible to inbreeding depression, were measures of growth based upon attained fish weight at a given age in each test situation examined: 147 day weight (0.0 to 19.1%), 364 day weight (6.2 to 62.8%), weight after 6 months in fishing pond (−4.6 to 25.4%), weight after 12 months in fishing pond (13.0 to 29.1%), 2-year male weight (11.3 to 55.3%), and 2-year female weight (10.2 to 57.0%). Other hatchery performance traits that showed inbreeding depression were: egg hatch-ability (−0.2 to 53.1%), fry survival (0.4 to 8.2%), feed conversion efficiency (5.0 to 9.0%), fish length at 2-years of age (4.7 to 36.9%), and egg mass produced at 2-years (12.1 to 57.0%). Field performance traits that yielded inbreeding depression were percent recovery of fish stocked (−2.5 to 41.1%) and biomass index (16.2 to 47.7%). Literature on the effects of inbreeding in fish populations is reviewed and the breeding approaches for controlling the rate of inbreeding accumulation in brood stock populations are outlined and discussed.

Aquaculture↗

The national coal-resources data system of the U.S. geological survey

The National Coal Resources Data System (NCRDS) was designed by the U.S. Geological Survey (USGS) to meet the increasing demands for rapid retrieval of information on coal location, quantity, quality, and accessibility. An interactive conversational query system devised by the USGS retrieves information from the data bank through a standard computer terminal. The system is being developed in two phases. Phase I, which currently is available on a limited basis, contains published areal resource and chemical data. The primary objective of this phase is to retrieve, calculate, and tabulate coal-resource data by area on a local, regional, or national scale. Factors available for retrieval include: state, county, quadrangle, township, coal field, coal bed, formation, geologic age, source and reliability of data, and coal-bed rank, thickness, overburden, and tonnage, or any combinations of variables. In addition, the chemical data items include individual values for proximate and ultimate analyses, BTU value, and several other physical and chemical tests. Information will be validated and deleted or updated as needed. Phase II is being developed to store, retrieve, and manipulate basic point source coal data (e.g., field observations, drill-hole logs), including geodetic location; bed thickness; depth of burial; moisture; ash; sulfur; major-, minor-, and trace-element content; heat value; and characteristics of overburden, roof rocks, and floor rocks. The computer system may be used to generate interactively structure-contour or isoline maps of the physical and chemical characteristics of a coal bed or to calculate coal resources. ?? 1976.

Computers & Geosciences↗

Isotopic composition of pyrite: Relationship to organic matter type and iron availability in some North American cretaceous shales

The S isotope composition of pyrite in Cretaceous shales from the Western Interior of North America is related to organic C abundance, kerogen type and Fe availability. Both calcareous and noncalcareous rocks show a correlation between S and C, but noncalcareous rocks are relatively enriched in S with a higher S/C ratio. This higher ratio probably shows that pyrite formation was Fe limited in the calcareous rocks. Organic-carbon-rich noncalcareous shales accumulated slowly beneath anoxic bottom waters. The anoxic bottom waters allowed hydrogen-rich organic matter to be preserved. Such shales have a narrow range of 34 S-depleted sulfide and have Fe/S ratios like stoichiometric pyrite, suggesting that pyrite formation in organic-rich shales was also limited by Fe availability. Conversely, organic-poor shales commonly accumulated at comparatively high rates, contain hydrogen-poor and refractory organic matter, and have a wide range of pyrite-S isotopic compositions. These organic-poor shales contain post-sulfidic authigenic minerals such as siderite and have excess reactive Fe rather than pyrite stoichiometry. Evidently Fe played a large role in early diagenesis and determined the course of post-sulfidic diagenesis. Fe availability was, however, mainly controlled by provenance, by the rates of sediment accumulation, and by the oxygen content of the depositional environment.

Chemical Geology: Isotope Geoscience Section↗

High-pressure deformation of calcite marble and its transformation to aragonite under non-hydrostatic conditions

We conducted deformation experiments on Carrara marble in the aragonite and calcite stability fields to observe the synkinematic transformation of calcite to aragonite, and to identify any relationships between transformation and deformation or sample strength. Deformation-induced microstructures in calcite crystals varied most significantly with temperature, ranging from limited slip and twinning at 400°C, limited recrystallization at 500°C, widespread recrystallization at 600 and 700°C, to grain growth at 800–900°C. Variations in confining pressure from 0.3 to 2.0 GPa have no apparent effect on calcite deformation microstructures. Aragonite grew in 10 −6 -10 −7 s −1 strain rate tests conducted for 18–524 h at confining pressures of 1.7–2.0 GPa and temperatures of 500–600°C. As in our previously reported hydrostatic experiments on this same transformation, the aragonite nucleated on calcite grain boundaries. The extent of transformation varied from a few percent conversion near pistons at 400°C, 2.0 GPa and 10 −4 s −1 strain rate in a 0.8 h long experiment, to 98% transformation in a 21-day test at a strain rate of 10 −7 s −7 , a temperature of 600°C and a pressure of 2.0 GPa. At 500°C, porphyroblastic 100–200 μm aragonite crystals grew at a rate faster than 8 × 10 −1 m s −1 . At 600°C, the growth of aragonite neoblasts was slower, ≈6 × 10 −1 m s −1 , and formed ‘glove-and-finger’ cellularprecipitation-like textures identical to those observed in hydrostatic experiments. The transformation to aragonite is not accompanied by a shear instability or anisotropic aragonite growth, consistent with its relatively small volume change and latent heat in comparison with compounds that do display those features.

Journal of Structural Geology↗

Geothermometry and water-rock interaction in selected thermal systems in the Cascade Range and Modoc Plateau, western United States

The sulfate—water isotope geothermometer indicates higher equilibrium temperatures than the silica or cation ratio geothermometers for the Na—Cl and Na—Ca—Cl thermal waters of the Cascade Range, Oregon and the Na—SO 4 thermal waters of the Modoc Plateau, northeastern California. Sulfate concentrations in the Na—Ca—Cl waters decrease as σ 18 O values of the dissolved sulfate become more depleted; conversely, sulfate concentrations in the Na—SO 4 waters increase as σ 18 O values of the sulfate become more depleted. Calculations show that the thermal waters are theoretically saturated with respect to anhydrite (CaSO 4 ) at temperatures very close to those calculated from the sulfate—water isotope geothermometer.

Geothermics↗

Transition of basaltic lava from pahoehoe to aa, Kilauea Volcano, Hawaii: Field observations and key factors

Nearly all Hawaiian basaltic lava erupts as pahoehoe, and some changes to aa during flowage and cooling; factors governing the transition involve certain critical relations between viscosity and rate of shear strain. If the lava slows, cools, and stops in direct response to concomitant increase in viscosity before these critical relations are reached, it remains pahoehoe. But, if flow mechanics (flow rate, flow dimensions, slope, momentum, etc.) impel the lava to continue to move and deform even after it has become highly viscous, the critical relations may be reached and the lava changes to aa. Typical modes of transition from pahoehoe to aa include: (1) spontaneous formation of relatively stiff clots in parts of the flowing lava where shear rate is highest; these clots grow into discrete, rough, sticky masses to which the remaining fluid lava incrementally adheres; (2) fragmentation and immersion of solid or semi-solid surface crusts of pahoehoe by roiling movements of the flow, forming cores of discrete, tacky masses; (3) sudden renewed movement of lava stored and cooled within surface reservoirs to form clots. The masses, fragments, and clots in these transition modes are characterized by spinose, granulated surfaces; as flow movement continues, the masses and fragments aggregate, fracture, and grind together, completing the transition to aa. Observations show that the critical relation between viscosity and rate of shear strain is inverse: if viscosity is low, a high rate of shear is required to begin the transition to aa; conversely, if viscosity is high, a much lower rate of shear will induce the transition. These relations can be demonstrated qualitatively with simple graphs, which can be used to examine the flow history of any selected finite lava element by tracing the path represented by its changing viscosity and shear rate. A broad, diffuse “transition threshold zone” in these graphs portrays the inverse critical relation between viscosity and shear rate; the transition to aa is represented by the path of the lava element crossing this zone. Moving lava flows can be regarded as natural viscometers, by which shear stress and rate of shear strain at selected points can be determined and viscosity can be computed. By making such determinations under a wide range of conditions on pahoehoe, aa, and transitional flow types, the critical relations that control the pahoehoe-aa transition can be quantified.

Hawaii↗

Sulfur and oxygen isotopic systematics of the 1982 eruptions of El Chichón Volcano, Chiapas, Mexico

Thermometers based on sulfur and oxygen isotopic compositions of anhydrite, pyrrhotite, titanomagnetite, and plagioclase crystals from fresh pumices of the 1982 eruptions of El Chichón Volcano indicate a pre-eruption temperature of 810 ± 40°C, confirming textural evidence that the anhydrite precipitated directly from the melt. The isotopic composition of sulfate leached from fresh ashfall samples shows it to be a mixture of anhydrite microphenocrysts and adsorbed sulfate derived from oxidized sulfur (SO 2 ) in the eruption plume. The leachate data show no evidence for rapid oxidation of significant amounts of H 2 S in the eruption cloud even though the fugacity ratio of H 2 S/SO 2 in the gas phase of the magma was >400. This may indicate kinetic inhibition of H 2 S to SO 2 conversion in the eruption cloud. Prior to eruption, the magma contained an estimated 2.6 wt. % sulfur (as SO 3 ). The estimated δ 34 S of the bulk magma is 5.8‰. Such a high value may reflect assimilation of 34 S-enriched evaporites or the prior loss of 34 S-depleted H 2 S to a fluid or gas phase during formation of a small prophyry-type hydrothermal system or ore deposit. In either case, the original magma must have been very sulfur rich. It is likely that the initial high sulfur content of the magma and at least some of its 34 S enrichment reflects involvement of subducted volcanogenic massive sulfides deposits during Benioff-zone partial melting. Isotopic data on mineralized, accidental lithic fragments support the possible development of a porphyry-type system at El Chichón.

Journal of Volcanology and Geothermal Research↗

Bathyal ostracodes from the Florida-Hatteras slope, the Straits of Florida, and the Blake Plateau

Epibathyal ostracodes from the Florida-Hatteras slope, the Blake Plateau and the Straits of Florida were studied to determine the relationship of numerous genera and species to bottom-water environmental conditions such as dissolved oxygen and bottom-water temperatures. From a total of 100 samples, 44 samples evenly distributed between 200 and 1100 m water depth and having an average of 325 specimens were examined in detail. Using occurrence data from the adjacent continental shelf, carapace preservation, Rose Bengal staining and population data, indigenous death assemblages were distinguished from transported or reworked fossil specimens. The percent of transported specimens varied as follows: Blake Plateau less than 1%; Straits of Florida 10–60%; Florida-Hatteras slope 1–15%. Indigenous death assemblages contained between 10 and 61 species per sample, averaging 33.3 species. Krithe, Argilloecia and Pseudocythere occur in greater than 90% of the samples and usually constitute 10 to 30% of each. Trachyleberidea, Bairdoppilata, Saida, Paranesidea, Ambocythere, Bythocypris, Cytherella, Bradleya, Henryhowella , and Polycopidae occur in 45 to 80% of the samples in varying percentages. The upper depth limits of 39 taxa occur at or just below the thermocline suggesting a relationship to temperature. Australoecia, Quasibuntonia, Cytheropteron, Ruggieriella, Saida, Ambocythere, Trachyleberidea, Macrocypris, Krithe, “Thalassocythere” , and Cytherella are most common or restricted to the O 2 minimum zone. Conversely, Anchistrocheles, Bradleya, Henryhowella , and Rockallia are most common below 750 m in well oxygenated water with temperatures below 8°C. The results show that: (1) ostracodes display a narrow depth zonation controlled by dissolved oxygen and water temperature; (2) species diversity is very high for a bathyal zone; (3) ostracodes can be used to identify the source of sediment that has been transported downslope; and (4) some taxa are useful in recognizing low oxygenated water in Cenozoic deposits.

Florida↗

The development of the continental margin of eastern North America-conjugate continental margin to West Africa

The continental margin of eastern North America was initiated when West Africa and North America were rifted apart in Triassic-Early Jurassic time. Cooling of the crust and its thinning by rifting and extension caused subsidence. Variation in amounts of subsidence led to formation of five basins. These are listed from south to north. (1) The Blake Plateau Basin, the southernmost, is the widest basin and the one in which the rift-stage basement took longest to form. Carbonate platform deposition was active and persisted until the end of Early Cretaceous. In Late Cretaceous, deposition slowed while subsidence persisted, so a deep water platform was formed. Since the Paleocene the region has undergone erosion. (2) The Carolina Trough is narrow and has relatively thin basement, on the basis of gravity modeling. The two basins with thin basement, the Carolina Trough and Scotian Basin, also show many salt diapirs indicating considerable deposition of salt during their early evolution. In the Carolina Trough, subsidence of a large block of strata above the flowing salt has resulted in a major, active normal fault on the landward side of the basin. (3) The Baltimore Canyon Trough has an extremely thick sedimentary section; synrift and postrift sediments exceed 18 km in thickness. A Jurassic reef is well developed on the basin's seaward side, but post-Jurassic deposition was mainly non-carbonate. In general the conversion from carbonate to terrigenous deposition, characteristics of North American Basins, occurred progressively earlier toward the north. (4) The Georges Bank Basin has a complicated deep structure of sub-basins filled with thick synrift deposits. This may have resulted from some shearing that occurred at this offset of the continental margin. Postrift sediments apparently are thin compared to other basins—only about 8 km. (5) The Scotian Basin, off Canada, contains Jurassic carbonate rocks, sandstone, shale and coal covered by deltaic deposits and Upper Cretaceous deeper water chalk and shale.

Journal of African Earth Sciences↗