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USGS1993

Distribution and conservation status of prairie dogs Cynomys mexicanus and Cynomys ludovicianus in Mexico

The two living species of black-tailed prairie dogs Cynomys mexicanus and C. ludovicianus are found in Mexico. Cynomys mexicanus , a Mexican endemic, is restricted to a 600-km2 region in northwestern Mexico. It is found in six large arid grassland valleys associated with gypsum soils and surrounded by arid scrub. Due to the small geographic range and destruction of its habitat this species is considered endangered. Cynomys ludovicianus is found in northwestern Mexico. Its present distribution comprises a very large complex covering approximately 55 000 ha, eight major dogtowns, and more than one million prairie dogs. Indeed, this population represents the largest continuous prairie dog complex left in North America. However, its present conservation status is considered as threatened, mainly because of the rapid deterioration of its habitat.

Biological Conservation↗

USGS1989

Oxygen isotope exchange kinetics of mineral pairs in closed and open systems: Applications to problems of hydrothermal alteration of igneous rocks and Precambrian iron formations

The systematics of stable-isotope exchange between minerals and fluids are examined in the context of modal mineralogical variations and mass-balance considerations, both in closed and in open systems. On mineral-pair ??18O plots, samples from terranes that have exchanged with large amounts of fluid typically map out steep positively-sloped non-equilibrium arrays. Analytical models are derived to explain these effects; these models allow for different exchange rates between the various minerals and the external fluids, as well as different fluid fluxes. The steep arrays are adequately modelled by calculated isochron lines that involve the whole family of possible exchange trajectories. These isochrons have initially-steep near-vertical positive slopes that rotate toward a 45?? equilibrium slope as the exchange process proceeds to completion. The actual data-point array is thus analogous to the hand of an "isotopic clock" that measures the duration of the hydrothermal episode. The dimensionless ratio of the volumetric fluid flux to the kinetic rate parameter ( u k) determines the shape of each individual exchange trajectory. In a fluid-buffered system ( u k ??? 1), the solutions to the equations: (1) are independent of the mole fractions of the solid phases; (2) correspond to Taylor's open-system water/rock equation; and (3) yield straight-line isochrons that have slopes that approach 1 f, where f is the fraction reacted of the more sluggishly exchanging mineral. The isochrons for this simple exchange model are closely congruent with the isochrons calculated for all of the more complex models, thereby simplifying the application of theory to actual hydrothermal systems in nature. In all of the models an order of magnitude of time (in units of kt) separates steep non-equilibrium arrays (e.g., slope ??? 10) from arrays approaching an equilibrium slope of unity on a ??-?? diagram. Because we know the approximate lifetimes of many hydrothermal systems from geologic and heat-balance constraints, we can utilize the 18O 16O data on natural mineral assemblages to calculate the kinetic rate constants (k's) and the effective diffusion constants (D's) for mineral-H2O exchange: these calculated values (kqtz ??? 10-14, kfeld ??? 10-13-10-12) agree with experimental determinations of such constants. In nature, once the driving force or energy source for the external infiltrating fluid phase is removed, the disequilibrium mineral-pair arrays will either: (1) remain "frozen" in their existing state, if the temperatures are low enough, or (2) re-equilibrate along specific closed-system exchange vectors determined solely by the temperature path and the mineral modal proportions. Thus, modal mineralogical information is a particularly important parameter in both the open- and closed-system scenarios, and should in general always be reported in stable-isotopic studies of mineral assemblages. These concepts are applied to an analysis of 18O 16O systematics of gabbros (Plagioclase-clinopyroxene and plagioclase-amphibole pairs), granitic plutons (quartz-feldspar pairs), and Precambrian siliceous iron formations (quartz-magnetite pairs). In all these examples, striking regularities are observed on ??-?? and ??-?? plots, but we point out that ??-?? plots have many advantages over their equivalent ??-?? diagrams, as the latter are more susceptible to misinterpretation. Using the equations developed in this study, these regularities can be interpreted to give semiquantitative information on the exchange histories of these rocks subsequent to their formation. In particular, we present a new interpretation indicating that Precambrian cherty iron formations have in general undergone a complex fluid exchange history in which the iron oxide (magnetite precursor?) has exchanged much faster with low-temperature (< 400??C) fluids than has the relatively inert quartz. ?? 1989.

Chemical Geology↗

USGS1991

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

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

Chemical Geology↗

USGS1968

SrRbK and Sr isotopic relationships in ultramafic rocks, southeastern Alaska

Geologic evidence suggests that a series of ultramafic complexes of the ‘Duke Island type’ located along a 560 km-long belt in southeastern Alaska crystallized from magmas of ultramafic composition. Some geologists have proposed that these magmas were derived by fractional fusion of ultramafic material in the upper mantle. The 87 Sr/ 86 Sr ratios, corrected for growth of radiogenic 87 Sr, in total rock samples and in minerals from four ultramafic complexes range from 0.7026 to 0.7068, and the K/Rb ratios in total rock samples range from 300 to 1200. Other workers have reported that the isotopic composition of strontium in alpine peridotites is significantly different from that of oceanic volcanic rocks, but the 87 Sr/ 86 Sr ratios of the Alaskan ultramafites and of oceanic volcanic rocks are similar.

Alaska↗

USGS1977

Mechanical and hydraulic properties of rocks related to induced seismicity

Witherspoon, P.A. and Gale, J.E., 1977. Mechanical and hydraulic properties of rocks related to induced seismicity. Eng. Geol., 11(1): 23-55. The mechanical and hydraulic properties of fractured rocks are considered with regard to the role they play in induced seismicity. In many cases, the mechanical properties of fractures determine the stability of a rock mass. The problems of sampling and testing these rock discontinuities and interpreting their non-linear behavior are reviewed. Stick slip has been proposed as the failure mechanism in earthquake events. Because of the complex interactions that are inherent in the mechanical behavior of fractured rocks, there seems to be no simple way to combine the deformation characteristics of several sets of fractures when there are significant perturbations of existing conditions. Thus, the more important fractures must be treated as individual components in the rock mass. In considering the hydraulic properties, it has been customary to treat a fracture as a parallel-plate conduit and a number of mathematical models of fracture systems have adopted this approach. Non-steady flow in fractured systems has usually been based on a two-porosity model, which assumes the primary (intergranular) porosity contributes only to storage and the secondary (fracture) porosity contributes only to the overall conductivity. Using such a model, it has been found that the time required to achieve quasi-steady state flow in a fractured reservoir is one or two orders of magnitude greater than it is in a homogeneous system. In essentially all of this work, the assumption has generally been made that the fractures are rigid. However, it is clear from a review of the mechanical and hydraulic properties that not only are fractures easily deformed but they constitute the main flow paths in many rock masses. This means that one must consider the interaction of mechanical and hydraulic effects. A considerable amount of laboratory and field data is now available that clearly demonstrates this stress-flow behavior. Two approaches have been used in attempting to numerically model such behavior: (1) continuum models, and (2) discrete models. The continuum approach only needs information as to average values of fracture spacing and material properties. But because of the inherent complexity of fractured rock masses and the corresponding decrease in symmetry, it is difficult to develop an equivalent continuum that will simulate the behavior of the entire system. The discrete approach, on the other hand, requires details of the fracture geometry and material properties of both fractures and rock matrix. The difficulty in obtaining such information has been considered a serious limitation of discrete models, but improved borehole techniques can enable one to obtain the necessary data, at least in shallow systems. The possibility of extending these methods to deeper fracture systems needs more investigation. Such data must be considered when deciding whether to use a continuum or discrete model to represent the interaction of rock and fluid forces in a fractured rock system, especially with regard to the problem of induced seismicity. When one is attempting to alter the pressure distribution in a fault zone by injection or withdrawal of fluids, the extent to which this can be achieved will be controlled in large measure by the behavior of the fractures that communicate with the borehole. Since this is essentially a point phenomenon, i.e., the changes will propagate from a relatively small region around the borehole, the use of a discrete model would appear to be preferable.

Engineering Geology↗

USGS1963

Spectrophotometric determination of micro quantities of zinc in rocks

A chemical method is presented for the determination of microgram amounts of zinc in rocks. Zinc is absorbed on anion-exchange resin from 1.2 M hydrochloric acid and eluted with 0.01 M hydrochloric acid. A diethyldithiocarbamate separation removes traces of interfering elements from the eluate. The zinc-diethyldithiocarbamate complex is extracted into chloroform at pH 8.5 and reextracted from other elements in the chloroform solution with 0.16 M hydrochloric acid and finally determined spectrophotometrically as the zincon complex at 621 mμ. The coefficient of variation of the method determined from replicate determinations of zinc on 75 selected samples of basalt, ranging in zinc content from 0.004 to 0.018 per cent, was found to be 6.3 per cent and essentially constant in the range of zinc content studied. This method of analysis has been used extensively for a study of zinc in basalts reported by Rader, Swadley, Huffman and Lipp (companion paper, 1963).

Geochimica et Cosmochimica Acta↗

USGS1986

Nd, O and Sr isotopic constraints on the origin of Precambrian rocks, southern Black Hills, South Dakota

The Nd, O and Sr isotopic characteristics of Precambrian metasedimentary, metavolcanic and granitic rocks from the Black Hills of South Dakota are examined. Two late-Archean granites (2.5-2.6 Ga) have T dm ages of 3.05 and 3.30 Ga, suggesting that at least one of the granites was derived through the melting of significantly older crust. Early-Proterozoic metasedimentary rocks have T dm ages that range from 2.32 to 2.45 Ga. These model ages, in conjunction with probable stratigraphic ages ranging from 1.9 to 2.2 Ga, indicate that mantle-derived material was added to the continental crust of this region during the early-Proterozoic. Previous studies of the Harney Peak Granite complex have reported U-Pb and Rb-Sr ages of about 1.71 Ga and most granite samples examined in this study have Sr isotopic compositions consistent with that age. Two granite samples taken from the same sill, however, give two-point Rb-Sr and Sm-Nd ages of 2.08 ±0.08 and 2.20 ±0.20Ga (∑ 2200 Nd = −15.5), respectively. In addition, whole-rock and apatite samples of the spatially associated Tin Mountain pegmatite give a Sm-Nd isochron age of 2000 ±100 Ma (∑ 2200 Nd = −5.8 ±1.8). The Sm-Nd, O and Rb-Sr isotopic systematics of these granitic rocks have been complicated to some degree by both crystallization and post-crystallization processes, and the age of the pegmatite and parts of the Harney Peak Granite complex remain uncertain. Processes that probably complicated the isotopic systematics of these rocks include derivation from heterogeneous source material, assimilation, mixing of REE between granite and country rock during crystallization via a fluid phase and post-crystallization mobility of Sr. The Nd isotopic compositions of the pegmatite and the Harney Peak Granite indicate that they were not derived primarily from the exposed metasedimentary rocks.

Geochimica et Cosmochimica Acta↗

USGS1990

High-density volatiles in the system C-O-H-N for the calibration of a laser Raman microprobe

Three methods have been used to produce high-density volatiles in the system C-O-H-N for the calibration of a laser Raman microprobe (LRM): synthetic fluid-inclusion, sealed fused-quartz-tube, and high-pressure-cell methods. Because quantitative interpretation of a Raman spectrum of mixed-volatile fluid inclusions requires accurate knowledge of pressure- and composition-sensitive Raman scattering efficiencies or quantification factors for each species, calibrations of these parameters for mixtures of volatiles of known composition and pressure are necessary. Two advantages of the synthetic fluid-inclusion method are that the inclusions can be used readily in complementary microthermometry (MT) studies and that they have sizes and optical properties like those in natural samples. Some disadvantages are that producing H 2 O-free volatile mixtures is difficult, the composition may vary from one inclusion to another, the exact composition and density of the inclusions are difficult to obtain, and the experimental procedures are complicated. The primary advantage of the method using sealed fused-quartz tubes is its simplicity. Some disadvantages are that exact compositions for complex volatile mixtures are difficult to predict, densities can be approximated only, and complementary MT studies on the tubes are difficult to conduct. The advantages of the high-pressure-cell method are that specific, known compositions of volatile mixtures can be produced and that their pressures can be varied easily and are monitored during calibration. Some disadvantages are that complementary MT analysis is impossible, and the setup is bulky. Among the three methods for the calibration of an LRM, the high-pressure-cell method is the most reliable and convenient for control of composition and total pressure. We have used the high-pressure cell to obtain preliminary data on 1. (1) the ratio of the Raman quantification factors for CH 4 and N 2 in an equimolar CH 4  N 2 mixture and 2. (2) the spectral peak position of ν 1 of CH 4 in that mixture, as well as in pure CH 4 , at pressures up to 690 bars. These data were successfully applied to natural inclusions from the Duluth Complex in order to derive their compositions and total pressures.

Geochimica et Cosmochimica Acta↗

USGS1992

Thermodynamics and kinetics of reactions involving vanadium in natural systems: Accumulation of vanadium in sedimentary rocks

A critical review of thermodynamic data for aqueous and solid V species is presented to evaluate dissolution, transport, and precipitation of V under natural conditions. Emphasis is given to results of experimental studies of V chemistry, especially those for which the experimental conditions are near those found in nature. Where possible, data are obtained for or corrected to the reference conditions of 298.15K, 1 atm (1.01325 bar) and zero ionic strength. Vanadium [IV] (V IV ) and vanadium[V] (V V ) are the most soluble forms of V in nature, and their complexes with fluoride, sulfate, and oxalate may act to increase V solubility under oxidizing conditions. Because redox behavior is of fundamental importance to understanding natural V chemistry, the kinetics of reduction of V IV to V III H 2 S were studied. Although H 2 S is predicted from thermodynamic data to be capable of reducing V IV to V III , this reaction has not been demonstrated experimentally. Experiments were carried out under conditions of temperature (45°C), pH (3.6–6.8), ionic strength (0.05–0.1 m), and V concentrations (9.8–240 μmolar) likely to be found in nature. Because the reaction is very slow, H 2 S concentrations in excess of natural conditions were used (8.1 × 10 −4 to 0.41 atm). The results show that V IV is reduced to V III under a variety of conditions. The rate increases with increasing pH, but is not appreciably affected by ionic strength (as represented by the concentration of KCl, which was used as the supporting electrolyte in all cases). Prior to initiation of the reaction, there is an induction period, the length of which increases with increasing KCl concentration or decreasing pH. Attempts to model the reaction mechanism by numerical methods have failed to produce a satisfying fit of the results, indicating partial reaction orders, a complex mechanism, or involvement of a variety of intermediate species. The results of the thermodynamic and kinetic studies were applied to understanding the genesis of V deposits such as those commonly found on the Colorado Plateau. Vanadium in these sandstone-hosted deposits is present mostly in the reduced oxidation state, V III . Because of the insolubility of V III oxyhydroxides, it is likely that a more oxidized form of V (either [IV] or [V]) was transported to the site of mineralization, and that the V was reduced in situ and subsequently precipitated. A probable reductant is hydrogen sulfide; the presence of pyrite cogenetic with the V minerals documents the presence of H 2 S during mineralization. The experiments described here show that H 2 S could have reduced V IV to V III , and thus led to the formation of these deposits.

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↗

USGS1994

Correlation of gold in siliceous sinters with 3He 4He in hot spring waters of Yellowstone National Park

Opaline sinter samples collected at Yellowstone National Park (YNP) were analyzed for gold by neutron activation and for other trace elements by the inductively coupled plasma optical emission spectroscopy (ICP-OES) method. No correlation was found between Au and As, Sb, or total Fe in the sinters, although the sample containing the highest Au also contains the highest Sb. There also was no correlation of Au in the sinter with the H 2 S concentration in the discharged hot spring water or with the estimated temperature of last equilibration of the water with the surrounding rock. The Au in rhyolitic tuffs and lavas at YNP found within the Yellowstone caldera show the same range in Au as do those outside the caldera, while thermal waters from within this caldera all have been found to contain relatively low dissolved Au and to deposit sinters that contain relatively little Au. Therefore, it is not likely that variations in Au concentrations among these sinters simply reflect differences in leachable Au in the rocks through which the hydrothermal fluids have passed. Rather, variations in [H 2 S], the concentration of total dissolved sulfide, that result from different physical and chemical processes that occur in different parts of the hydrothermal system appear to exert the main control on the abundance of Au in these sinters. Hydrothermal fluids at YNP convect upward through a series of successively shallower and cooler reservoirs where water-rock chemical and isotopic reactions occur in response to changing temperature and pressure. In some parts of the system the fluids undergo decompressional boiling, and in other parts they cool conductively without boiling. Mixing of ascending water from deep in the system with shallow groundwaters is common. All three processes generally result in a decrease in [H 2 S] and destabilize dissolved gold bisulfide complexes in reservoir waters in the YNP system. Thus, different reservoirs in rocks of similar composition and at similar temperatures may contain waters with different [H 2 S] and [Au]. The [H 2 S] in a subsurface reservoir water is difficult to assess on the basis of analyses of hot spring waters because of uncertainties about steam loss during fluid ascent. However, the same processes that result in low [H 2 S] in reservoir waters also tend to result in decreases in the ratio of 3 He 4 He(R) "> 3He4He(R) dissolved in that water. Values of R relative to this ratio in air ( Ra ) attain values > 15 in YNP thermal waters. To date, all of the thermal waters at YNP that have R Ra "> RRa values <9 have been found to deposit sinters with relatively low gold concentrations. These include all of the thermal waters that discharge from 180–215°C reservoirs at Upper, Midway, and Lower Geyser Basins within the western part of the Yellowstone caldera, and thermal waters at Norris Geyser Basin, outside the Yellowstone caldera, where some of the waters flow directly to the surface from a reservoir where the temperature is about 300°C. A high 3 He 4 He "> 3He4He ratio in thermal water discharged at the surface does not guarantee high gold concentrations in the sinter deposited by this water. Boiling with loss of steam (the gas phase takes a separate route to the surface) during rapid upflow from the shallowest reservoir to the surface decreases the [H 2 S] and total He dissolved in the residual liquid without appreciably changing the 3 He 4 He "> 3He4He ratio. This is because the isotopic composition of the He of the initial bulk fluid is unchanged and there is too little time for much radiogenic 4 He to build back into the liquid during this rapid ascent from the near-surface reservoir. However, if boiling with phase separation and loss of steam occurs deep in the system, the 3 He 4 He "> 3He4He ratio in the residual liquid, now depleted in H 2 S and total He, will be susceptible to dilution with radiogenic 4 He that is acquired during the longer residence time underground. Some or all of the Au that comes out of solution when an initial gold bisulfide complex breaks down as a result of loss of H 2 S may be swept up to the surface as solid (probably colloidal) particles, depending on the rate of flow of the mixture of water and steam, and the geometry of the channel. Where colloidal silica also forms as a result of this boiling, free Au apparently becomes attached to the colloidal silica and deposits where the silica deposits.

Wyoming↗

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↗

USGS1990

Volcanism in Northwest Ishtar Terra, Venus

Soviet Venera 15/16 radar images and topographic data for an area in NW Ishtar Terra, Venus (74°N, 313°E) contain evidence for the existence of a complex volcanic center. Located at the intersection of Akna and Freyja Montes (both elevated ∼4 to 7 km above the planetary reference radius of 6051 km), this volcanic center has a complex caldera system, possibly more than one major eruptive vent, and associated lava flows at lower elevations. Evidence for a volcanic center at NW Ishtar Terra includes: a smooth-surfaced unit with moderate radar brightness; adjacent (possibly associated) bright flows extending northwestward more than 300 km; an irregularly shaped depression 200 by 250 km in size and ∼2.0 km deep; arcuate slopes that appear to mark the rims of several semicircular depressions within the larger depression; and 5.5-km-elevation ridge separating volcanic deposits of northern Lakshmi Planum from those of NW Ishtar Terra. The lack of a notable shield construct at NW Ishtar and the similarity between smooth terrain and undivided plains of Lakshmi Planum suggest that volcanic units at NW Ishtar Terra may represent an earlier (perhaps younger) stage of volcanism than that attributed to Colette and Sacajawea Paterae of Lakshmi Planum. A westward migration in volcanic activity from Sacajewea to Colette NW Ishtar is supported by relative youth of Colette as compared to Sacajawea, the relatively young stage of volcanism at NW Ishtar Terra, and the superposition of this volcano on the banded terrain of Akna and Freyja Montes.

Icarus↗

USGS1990

Liquid-chromatography thermospray mass-spectrometric study of n-acylamino dilactones and 4-butyrolactones derived from Antimycin-A

Reversed-phase high-performance liquid chromatography—thermospray mass spectrometric (HPLC—MS) characteristics of four sets of lactonic complexes (one 4-butyrolactones and three dilactone complexes) derived from antimycin A were investigated. Three types of 8-hydroxy analogues were also included in the study. Pairs of a–b structures isomeric at the 8-acyloxy ester side-chains were best separated with a high-efficiency octadecylsilica column prior to analysis by HPLC—MS. Mass spectra of the a–b pairs each with identical molecular weights exhibited virtually indistinguishable fragmentation patterns, although their relative intensities were not superimposable. In some cases, HPLC—MS of the title compounds yielded mass chromatograms showing the minor components more easily recognizable than the HPLC—UV counter parts because of the apparent higher ionization efficiency of the minor isomers and increased resolution of subcomponents in the MS system. Under the mobile phase conditions employed, analyte ionization occurred with variable degrees of gas phase ammonolysis depending upon the ammonia concentration of the buffer. Potential applicability of the on-line HPLC—MS technique for the characterization of components in mixtures of antimycin analogues and isomers is demonstrated.

Journal of Chromatography↗

USGS1990

Sedimentary evolution of the Pliocene and Pleistocene Ebro margin, northeastern Spain

The Pliocene and Pleistocene deposits of the Spanish Ebro margin overlie a regional unconformity and contain a major disconformity. These unconformities, named Reflector M and Reflector G, mark the bases of two seismic sequences. Except for close to the upper boundary where a few small channel deposits are recognized, the lower sequence lacks channels. The upper sequence contains nine channel-levee complexes as well as base-of-slope aprons that represent the proximal part of the Valencia turbidite system. Diverse geometries and variations in seismic units distinguish shelf, slope, base-of-slope and basin-floor facies. Four events characterize the late Miocene to Pleistocene evolution of the Ebro margin: (a) formation of a paleodrainage system and an extensive erosion-to-depositional surface during the latest Miocene (Messinian), (b) deposition of hemipelagic units during the early Pliocene, (c) development of canyons during the late Pliocene to early Pleistocene, and (d) deposition of slope wedges, channel-levee complexes, and base-of-slope aprons alternating with hemipelagic deposition during the Pleistocene. Sea-level fluctuations influenced the evolution of the sedimentary sequences of the Ebro margin, but the major control was the sediment supply from the Ebro River.

Marine Geology↗

USGS1990

Factors controlling late Cenozoic continental margin growth from the Ebro Delta to the western Mediterranean deep sea

The Ebro continental margin sedimentation system originated with a Messinian fluvial system. This system eroded both a major subaerial canyon cutting the margin southeastward from the present Ebro Delta and an axial valley that drained northeastward down Valencia Trough. Post-Messinian submergence of this topography and the Pliocene regime of high sea levels resulted in a marine hemipelagic drape over the margin. Late Pliocene to Pleistocene glacial climatic cycles, drainagebasin deforestation, and sea-level lowstands combined to increase sediment supply, cause the margin to prograde, and create a regime of lowstand sediment-gravity flows in the deeper margin. The depositional patterns of regressive, transgressive and highstand sea-level regimes suggest that location of the sediment source near the present Ebro Delta throughout the late Cenozoic, southward current advection of sediment, and greater subsidence in the southern margin combined to cause generally asymmetric progradation of the margin to the southeast. Thicker, less stable deposits filling the Messinian subaerial canyon underwent multiple retrograde failures, eroded wide gullied canyons and formed unchanneled base-of-slope sediment aprons in the central margin area; other margin areas to the north and south developed a series of channel-levee complexes. On the basin floor, the formation of Valencia Valley over the Messinian subaerial valley and earlier faults led to draining of about 20% of the Ebro Pleistocene sediment from channel-levee complexes through the valley to prograde Valencia Fan as much as 500 km northeast of the margin. Thus, the Ebro margin has two growth directions, mainly southeastward during higher sea levels, and eastward to northeastward during lower sea levels. The northeastward draining of turbidity currents has produced unusually thin and widely dispersed turbidite systems compared to those on ponded basin floors. During the past few centuries, man's impact has exceeded natural controls on Ebro margin growth. Deforestation of the drainage basin more than doubled the normal Holocene sediment supply, and construction of dams then reduced the supply by 95%. This reduction of the past 50 years has caused erosion of the delta and contamination of bottom sediment because normal Holocene sediment discharge is not available to prograde the delta or help dilute pollutants.

Marine Geology↗

USGS1995

Fate, bioavailability and toxicity of silver in estuarine environments

The chemistry and bioavailability of Ag contribute to its high toxicity in marine and estuarine waters. Silver is unusual, in that both the dominant speciation reaction in seawater and the processes important in sorbing Ag in sediments favour enhanced bioavailability. Formation of a stable chloro complex favours dispersal of dissolved Ag, and the abundant chloro complex is available to biota. Sequestration by sediments also occurs, but with relatively slow kinetics. Amorphous aggregated coatings enhance Ag accumulation in sediments, as well as Ag uptake from sediments by deposit feeders. In estuaries, the bioaccumulation of Ag increases 56-fold with each unit of increased Ag concentration in sediments. Toxicity for sensitive marine species occurs at absolute concentrations as low as those observed for any nonalkylated metal, partly because bioaccumulation increases so steeply with contamination. The environmental window of tolerance to Ag in estuaries could be narrower than for many elements.

Marine Pollution Bulletin↗

USGS1981

Lower Eocene alluvial paleosols (Willwood Formation, Northwest Wyoming, U.S.A.) and their significance for paleoecology, paleoclimatology, and basin analysis

The lower Eocene Willwood Formation of northwest Wyoming is a 700 m thick accumulation of alluvial floodplain and channel mudstones and sandstones, nearly all of which show paleopedogenic modifications. Pedogenesis of Willwood sandstones is indicated by taproot and vertebrate and invertebrate bioturbation, early local cementation by calcium carbonate, and thin illuviation cutans on clastic grains. Pedogenesis in Willwood mudstones is indicated by plant bioturbation, insect and other invertebrate burrow casts and lebensspuren; free iron, aluminum, and manganese mobilization, including hydromorphic gleying; sesquioxide and calcareous glaebule formation in lower parts of the solum; presence of clay-rich and organic carbon-rich zones; and well differentiated epipedons and albic and spodic horizons. Probable A horizons are also locally well developed. Occurrence of variegated paleosol units in thick floodplain mudstone deposits and their association with thin, lenticular, and unconnected fluvial sandstones in the Willwood Formation of the central and southeast Bighorn Basin suggest that these soils formed during times of rapid sediment accumulation. The tabular geometry and lateral persistence of soil units as well as the absence of catenization indicate that Willwood floodplains were broad and essentially featureless. All Willwood paleosols were developed on alluvial parent materials and are complex in that B horizons of younger paleosols were commonly superimposed upon and mask properties of suspected A and B horizons of the next older paleosols. The soils appear to be wet varieties of the Spodosol and Entisol groups (aquods and ferrods, and aquents, respectively), though thick, superposed and less mottled red, purple, and yellow paleosols resemble some ultisols. Most Willwood paleosols resemble warm temperate to subtropical alluvial soils that form today under alternating wet and dry conditions and (or) fluctuating water tables. The up-section decrease in frequency of gley mottles, increase in numerical proportion and thickness of red versus orange coloration, and increase in abundance of calcrete glaebules indicate better drained soils and probably drier climate in late Willwood time. This drying is believed to be related to creation of rain shadows and spacing of rainfall (but not necessarily decrease in absolute rainfall) due to progressive tectonic structural elevation of the mountainous margins of the Bighorn Basin.

Wyoming↗