Kinetics of reactions between aqueous sulfates and sulfides in hydrothermal systems

The rates of chemical reactions between aqueous sulfates and sulfides are essentially identical to sulfur isotopic exchange rates between them, because both the chemical and isotopic reactions involve simultaneous oxidation of sulfide-sulfur atoms and reduction of sulfate-sulfur. The rate of reaction can be expressed as a second order rate law: R = k·[∑SO₄^2?]·[∑S^2?], where R is the overall rate, k is the rate constant and [∑SO₄^2?] and [∑S^2?] are molal concentrations. We have computed the rate constants from the available experimental data on the partial exchange of sulfur isotopes between aqueous sulfates and sulfides using the rate law established by us: $\text{ln(}\text{α}{}^{\mathrm{e}}\text{? α}\text{α}{}^{\mathrm{e}}\text{? α}{}^0\text{) = ? kt([∑SO}{}_4{}^{\mathrm{2?}}\text{] + [∑S}{}^{\mathrm{2?}}\text{])}$, where t is time and α⁰, α, and α^e are, respectively, the fractionation factors at t = 0 (the initial condition), at the end of experiment, and at equilibrium. The equilibrium fractionation factor can be expressed as: $\text{1000 ln α}{}^{\mathrm{e}}\text{=}\text{6.463 × 10}{}^6\text{T}{}^2\text{+ 0.56 (±.5)}$ (T in Kelvin).The rate constants are strongly dependent on T and pH, but not in as simple a manner as suggested by Igumnov (1976). Our rate constants in Na-bearing hydrothermal solutions decrease by 1 order of magnitude with an increase in pH by 1 unit at pH's less than ~3, remain constant in the pH range of ~4 to ~7, and again decrease at pH >7. The activation energy for the reaction also depends on pH: 18.4 ± 1 kcal/mole at pH = 2, 29.6 ± 1 kcal/mole at pH = 4 to 7, and between 40 and 47 kcal/mole at pH around 9. The observed pH dependence of the rate constant and of the activation energy can be best explained by a model involving thiosulfate molecules as reaction intermediates, in which the intramolecular exchange of sulfur atoms in thiosulfates becomes the rate determining step.The rate constants obtained in this study were used to compute the changes in the isotopic fractionation factors between aqueous sulfates and sulfides during cooling of fluids. Comparisons with data of coexisting sulfate-sulfide minerals in hydrothermal deposits, suggest that simple cooling was not a likely mechanism for coprecipitation of sulfate and sulfide minerals at temperatures below 350°C. Mixing of sulfide-rich solutions with sulfate-rich solutions at or near the depositional sites is a more reasonable process for explaining the observed fractionation.The degree of attainment of chemical equilibrium between aqueous sulfates and sulfides in a hydrothermal system, and the applicability of a_O2-pH type diagrams to mineral deposits, depends on the ∑S content and the thermal history of the fluid, which in turn is controlled by the flow rate and the thermal gradient in the system.The rates of sulfate reduction by non-bacterial processes involving a variety of reductants are also dependent on T, pH, [∑SO₄^2?], and [∑S^2?], and appear to be fast enough to become geochemically important at temperatures above about 200°C.     

Carbonate platform depositional sequences, Upper Cretaceous, south-central Pyrenees (Spain)

The Upper Cretaceous (Cenomanian-Maastrichtian) of the south-central Pyrenees shows five carbonate platform sequences where the major parameters are tectonism, relative sea-level fluctuations and inherited depositional profile. Depositional geometries and basin analysis permit an understanding of the depositional history.Five depositional sequences have been recognized: (1) The Santa Fe sequence (Middle-Upper Cenomanian), a ramp to a skeletal rimmed shelf with an escarpment bypass margin. The lower boundary is an angular unconformity and the upper one records a sea-level drop. The platform location of the margin was determined by a listric normal fault. (2) An abrupt sea-level rise drowned the former platform. The Congost sequence (Turonian-Lower Coniacian), a distally steepened ramp with erosional distal deep slope. The depositional model was largely controlled by pre-existing basin morphology. Cessation of platform development was due to a relative sea-level drop. (3) The Sant Corneli sequence (Upper Coniacian-Lower Santonian), a mixed terrigenous-skeletal homoclinal ramp with upright margin, deep slope and dysaerobic basin. The slope results from the backstepping by 24 km of the previous margin and gentle basin tilting. The platform margin remained more or less at the same position, and relief between platform and slope increased indicating continuous relative sea-level rise. The upper boundary is an angular unconformity at the platform margin produced by an abrupt sea-level rise and platform drowning, and by listric normal faulting. (4) The Vallcarga sequence (Upper Santonian-Campanian), a distal-steepened skeletal homoclinal ramp, erosional escarpment and turbidite basin, which corresponds to the Mesozoic maximum marine expansion. A listric normal fault created two depositional areas: a more or less flat footwall block with a north-northwest prograding carbonate ramp.     

Granulite-amphibolite facies metasediments from the Serre (Calabria,Southern Italy): their protoliths and the processes controlling their chemistry

In the northwestern Serre, a near continuous section through the Palaeozoic lower continental crust crops out. This paper deals with granulite facies metasedimentary rocks of this section. Fifty-five chemical analyses (major elements, Sc, V, Cr, Co, Ni, Rb, Sr, Y, Nb and Ba) are given. Chemical data indicate that the original sedimentary sequence was made up of arenites in the lower part and mainly Fe and Mg rich pelites in the upper part. The metapelites experienced anatexis and removal of some melt, whereas the meta-arenites suffered only incipient anatexis and became dehydration granulites. The various rock types display an overall relatively low K/Rb ratio due mainly to the stability of K- and Rb-retaining phases. A weighted mean composition of the fragment of the lower continental crust outcropping in the Serre has been established by integrating the chemical data for metasediments (55 analyses), metabasites (92 analyses) and dioritic and tonalitic gneisses (10 analyses) with the field data. This composition compared to the compositions of the bulk continental crust and of other sections considered as belonging to the lower crust, confirms the hypothesis that (1) the lower crust is heterogeneous, and (2) it is more basic than the continental crust.     

Sulla determinazione e sul calcolo dell'umidità dell'aria

Riassunto Premessi alcuni cenni generali sul calcolo e sulla determinazione del-l'umidità, l'A., col metodo dei minimi quadrati, perviene ad una formula in base alla quale, dalla lettura dei due termometri, asciutto e bagnato, si può ricavare direttamente l'umiditá relativa ed il deficit di saturazione senza l'aiuto di alcuna tabella. Procede quindi alla costruzione di due nomogrammi che facilitano notevolmente tali determinazioni.

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Summary After previously stating some general accounts about the calculation and determination of the air-dampness, the Autor, using the least square method, gets to a formula, according to which, by reading the two thermometers, dry and damp the relative dampness and the saturation-deficit can be directly drawn up without the help of any table. Afterwards he gets on constructing two nomograms that make remarkably easy such determinations. *** DIRECT SUPPORT *** A2919023 00003

     

Mesozoic extension in the Basque–Cantabrian basin (N Spain): Contributions from AMS and brittle mesostructures

In this work we analyse and check the results of anisotropy of magnetic susceptibility (AMS) by means of a comparison with palaeostress orientations obtained from the analysis of brittle mesostructures in the Cabuérniga Cretaceous basin, located in the western end of the Basque–Cantabrian basin, North Spain. The AMS data refer to 23 sites including Triassic red beds, Jurassic and Lower Cretaceous limestones, sandstones and shales. These deposits are weakly deformed, and represent the syn-rift sequence linked to basins formed during the Mesozoic and later inverted during the Pyrenean compression. The observed magnetic fabrics are typical of early stages of deformation, and show oblate, triaxial and prolate magnetic ellipsoids. The magnetic fabric seems to be related to a tectonic overprint of an original, compaction, sedimentary fabric. Most sites display a NE–SW magnetic lineation that is interpreted to represent the stretching direction of the Early Cretaceous extensional stage of the basin, without recording of the Tertiary compressional events, except for sites with compression-related cleavage.Brittle mesostructures include normal faults, calcite and quartz tension gashes and joints, related to the extensional stage. The results obtained from joints and tension gashes show a dominant N–S to NE–SW, and secondary NW–SE, extension direction. Paleostresses obtained from fault analysis (Right Dihedra and stress inversion methods) indicate NW–SE to E–W, and N–S extension direction. The results obtained from brittle mesostructures show a complex pattern resulting from the superposition of several tectonic processes during the Mesozoic, linked to the tectonic activity related to the opening of the Bay of Biscay during the Early Cretaceous. This work shows the potential in using AMS analysis in inverted basins to unravel its previous extensional history when the magnetic fabric is not expected to be modified by subsequent deformational events. Brittle mesostructure analysis seems to be more sensitive to far-field stress conditions and record longer time spans, whereas AMS records deformation on the near distance, during shorter intervals of time.     

Association of subsurface radon changes in Alaska and the northeastern United States with earthquakes

Changes of radon concentration in the ground have been reported to correlate with seismic activity in many places over widely varying distances from the earthquake epicenters, sometimes over 100's and occasionally over 1000's of km depending on the magnitude M of the earthquakes. For proper use of such correlations in forecasting the location and size of impending earthquakes, it would be useful to establish a relation between M and the maximum distance x_M at which radon can be significantly altered by preseismic effects.We have monitored radon in the ground continuously at Blue Mountain Lake, NY starting Dec. 3. 1975 and at three locations in Alaska—Icy Bay, Yakataga, and Sand Point (starting Nov. 12, 1979; March 5, 1980; and June 29, 1980 respectively). Sample correlations from visual examination of the recent radon record and tentative use of a proposed scaling relation show a number of possible earthquake-related signals at these locations. The data are compatible with scaling relations that were derived from two separate models of premonitory elastic strains. In this work x_M = 10^0.48M, where x_M is in units of km and M ≥ 3. Since tilt and strain signals correlate similarly with magnitude and distance, it is likely that most earthquake-related radon signals are mechanically induced.     

Validation of Landslide Susceptibility Maps; Examples and Applications from a Case Study in Northern Spain

A procedure for validating landslide susceptibility maps wasapplied in a study area in northern Spain and the results obtained compared. Validationwas used to carry out sensitivity analysis for individual variables and combinationsof variables. The validity of different map-making methods was tested, as well as theutility of different types of Favourability Functions. The results obtained show thatvalidation is essential to determine the predictive value of susceptibility maps. Italso helps to better select the most suitable function and significant variables, thus improving the efficiency of the mapping process. Validation based on a temporal strategy makes it possible to derive hazard maps from susceptibility maps.     

Strategic groundwater resources in the Tagliamento River basin (northern Italy): hydrogeological investigation integrated with geophysical exploration

The western sector of the Tagliamento River basin (Friuli Venezia-Giulia Region; northern Italy) is characterized by important water resources, both superficial and underground. In particular, in the Quaternary deposits of the plain, up to a depth of 500 m, six artesian aquifer systems exist. A large amount of lithological, geomorphological, and hydrogeological data is presented, allowing for definition of (a) the principal aquifer system of the area to a depth of about 500 m; (b) geometrical characteristics of the aquifers (thickness, lateral extension, etc); (c) the hydraulic parameters (hydraulic conductivity, transmissivity); (d) chemico-physical characteristics of the water; and (e) vulnerability to pollution of the aquifer systems. In a test area, where many boreholes were drilled for fresh water supply, the conceptual hydrogeological model was integrated by a detailed and repeated three-dimensional (3D) resistivity survey using combined electrical resistivity tomography (ERT) and time-domain electromagnetic (TDEM) soundings. ERT investigation was mainly used to get detailed information about geometry and porosity of the overburden and to calibrate the shallowest TDEM information.     

Crystallization conditions of Los Angeles, a basaltic Martian meteorite

The texture of Los Angeles (stone 1) is dominated by relatively large (0.5−2.0 mm) anhedral to subhedral grains of pyroxene, and generally subhedral to euhedral shocked plagioclase feldspar (maskelynite). Minor phases include subhedral titanomagnetite and ilmenite, Fe-rich olivine, olivine+augite-dominated symplectites [some of which include a Si-rich phase and some which do not], pyrrhotite, phosphate(s), and an impact shock-related alkali- and silica-rich glass closely associated with anhedral to euhedral silica grains. Observations and model calculations indicate that the initial crystallization of Mg-rich pigeonitic pyroxenes at ≤1150 °C, probably concomitantly with plagioclase, was followed by pigeonitic and augitic compositions between 1100 and 1050 °C whereas between 1050 and 920 to 905 °C pyroxene of single composition crystallized. Below 920 to 905 °C, single composition Fe-rich clinopyroxene exsolved to augite and pigeonite. Initial appearance of titanomagnetite probably occurred near 990 °C and FMQ-1.5 whereas at and below 990 °C and ≥FMQ-1.5 titanomagnetite and single composition Fe-rich clinopyroxene may have started to react, producing ilmenite and olivine. However, judging from the most common titanomagnetite compositions, we infer that most of this reaction likely occurred between 950 and 900 °C at FMQ-1.0±0.2 and nearly simultaneously with pyroxene exsolution, thus producing assemblages of pigeonite, titanomagnetite, olivine, ilmenite, and augite. We deem this reaction as the most plausible explanation for the formation of the olivine+augite-dominated symplectites in Los Angeles. But we cannot preclude possible contributions to the symplectites from the shock-related alkali- and silica-rich glass or shocked plagioclase, and the breakdown of Fe-rich pigeonite compositions to olivine+augite+silica below 900 °C. Reactions between Fe-Ti oxides and silicate minerals in Los Angeles and other similar basaltic Martian meteorites can control the T-fO₂ equilibration path during cooling, which may better explain the relative differences in fO₂ among the basaltic Martian meteorites.     

Sub-wavebase cross-bedded grainstones on a distally steepened carbonate ramp, Upper Miocene, Menorca, Spain

Cross‐bedded grainstones on carbonate ramps and shelves are commonly related to the locus of major wave energy absorption such as shorelines, shoals or shelf breaks. In contrast, on the Early Tortonian carbonate platform of Menorca (Balearic Islands), coarse‐grained, cross‐bedded grainstones are found at a distance from the palaeoshoreline where they were deposited below the wavebase. Excellent exposures along continuous outcrops on the sea cliffs of Menorca reveal the depositional profile and three‐dimensional distribution of the different facies belts of the Tortonian ramp depositional system. Basinward from the palaeoshoreline, fan deltas and beach deposits pass into 5‐km‐wide gently dipping bioturbated dolopackstone (inner and middle ramp), then into 12–20°‐dipping dolograinstone/rudstone clinobeds (ramp slope) and, finally, into subhorizontal fine‐grained basinal dolowackestone to dolopackstone (outer ramp). In this Miocene example, coarse‐grained grainstones exist in five different settings other than beach deposits: (1) on the middle ramp, where cross‐bedded grainstones were deposited by currents roughly parallel to the shoreline at 40–70 m estimated water depth and are interbedded with gently dipping bioturbated dolomitized packstones; (2) on the upper slope, where clinobeds are composed mostly of in situ rhodoliths and red‐algae fragments; (3) on the lower slope, as small‐scale bedforms (small three‐dimensional subaqueous dunes) migrating parallel to the slope; (4) at the transition between the lower slope and the outer ramp, where mollusc‐rich and rhodolithic rudstones and grainstones, interbedded in dolomitized laminated wackestones containing abundant planktonic foraminifera, infill slide/slump scars as upslope‐backstepping bodies (backsets); (5) at the toe of the slope, where coarse skeletal grainstones indicate bedform migration parallel to the platform margin, induced by currents at more than 150 m estimated water depth. This Late Miocene example also illustrates how changes in intrabasinal environmental conditions (nutrients and/or temperature) may produce changes in stratal patterns and facies architecture if they affect the biological system. Two depositional sequences compose the Miocene platform on Menorca, where a reef‐rimmed platform prograded onto an earlier distally steepened ramp. The transition from the ramp to the reef‐rimmed platform was effected by an increase in accommodation space caused by ecological changes, promoting a shift from a grain‐ to a framework‐producing biota.