Arrens Zn (Pb), Ba Devonian deposit,Pyrénées,France: an exhalative-sedimentary-type deposit similar to Meggen

The Perrefitte anticlinorium district in the Paleozoïc province of the Pyrenees contains abundant mineral occurrences, prospects, and old mines in the upper volcano-sedimentary layer of the Ordovician and Devonian sediments which have been metamorphosed in the greenschist to amphibolite facies. Although of different lithologic environments, the mineralization shows, as everywhere in the Pyrenees, many common characteristics. However, the Arrens deposit outcropping over 5 km on both limbs of a syncline displays specific characteristics: abundant barite with lateral Zn (Pb) Ba zoning, exceptionally thick subreef (?) footwall limestone overlain by black siltstone, abundant Ba silicate, in particular celsianite, locally cymrite, and siliceous, sedimentary-hydrothermal gangue. Due to deformation, such as tight folds and flow cleavage, the paleogeography of the Arrens geological environment could not be precisely reconstructed. However, the deposit is very likely located in an unstable shelf zone. Lithology underwent many changes close to the synsedimentary faults including at Arrens a limestone shelf facies and some small basins of black siltstone, at the bottom of which mineralization occurs. As all the mineralization of the Pyrenees Paleozoic, the deposit is of the exhalative or hydrothermal sedimentary type and bears some analogies with other exhalative deposits throughout the world. (The word “exhalative” is etymologically related to gases. Although “hydrothermal” is a more exact word as it pertains to hot water, “exhalative” will be used in this paper, being of most current usage.)     

Infrared estimates of aliphatic kerogen carbon in sedimentary rocks

An infrared routine has been developed to estimate the aliphatic portion of kerogen carbon in sedimentary rocks. The procedure does not require isolation of the organic matter and is based on a computer-assisted determination of global band areas in the region of the aliphatic carbon-hydrogen stretching vibrations around 2900cm⁻¹. From these integrated absorptions the amount of aliphatic carbon C_al (mg of aliphatic carbon per gram of solvent-extracted rock) is calculated by means of a calibration with model rocks. Carbonate overtones which interfere in the case of limestones are eliminated by comparison to a CaCO₃ standard.The method has been applied to rocks containing kerogens of different types and maturities at TOC levels of 0.5 to 12%. The aliphatic carbon concentrations range from 0.5 to 60mg·g⁻¹ and correlate reasonably well with the residual genetic potentials of the rocks as measured by S₂ values from Rock-Eval pyrolysis. The ratio S₂/C_al is found to decrease with burial depth reflecting a maturity enhanced conversion of aliphatic carbon to fixed aromatic carbon under Rock-Eval conditions.     

Spinelloid phases in the system MgGa2O4-Mg2GeO4

Spinelloid phases have been observed and characterized by powder X-ray diffraction and high-resolution electron microscopy. Mg₃Ga₂GeO₃(III), with a narrow composition range of approximately 3 mole percent Mg₂GeO₄, is stable at atmospheric pressure up to about 1,420° C, and is isostructural with β-Mg₂SiO₄ and the spinelloid Phase III of the NiAl₂O₄-Ni₂SiO₄ system. This represents the first occurrence of a β-phase structure stable at 1 atm pressure. Above 1,420° C (1 atm) Mg₃Ga₂GeO₈ (III) decomposes reversibly into a mixture of spinel and olivine. At high pressure (around 30 kbar at 1,100° C) it transforms into another spinelloid phase, Mg₃Ga₂GeO₈ (IV), isostructural with Phase IV of the NiAl₂O₄-Ni₂SiO₄ system. In terms of crystal structures and phase relations therefore there exists a close analogy between the magnesium gallo-germanate and nickel alumino-silicate systems, the former being a lower-pressure analogue of the latter. Our investigation of a number of other pseudo-binary spinel-olivine oxide systems suggests that the formation of spinelloid phases can be associated with the inverse character of the spinel component.     

Seasonal distributions of suspended particulate material and dissolved nutrients in a coastal plain estuary

The temporal and spatial distributions of salinity, dissolved oxygen, suspended particulate material (SPM), and dissolved nutrients were determined during 1983 in the Choptank River, an estuarine tributary of Chesapeake Bay. During winter and spring freshets, the middle estuary was strongly stratified with changes in salinity of up to 5‰ occurring over 1 m depth intervals. Periodically, the lower estuary was stratified due to the intrusion of higher salinity water from the main channel of Chesapeake Bay. During summer this intrusion caused minimum oxygen and maximum NH₄ ⁺ concentrations at the mouth of the Choptank River estuary. Highest concentrations of SPM, particulate carbon (PC), particulate nitrogen (PN), total nitrogen (TN), total phosphorous (TP) and dissolved inorganic nitrogen (DIN) occurred in the upper estuary during the early spring freshet. In contrast, minimum soluble reactive phosphate (SRP) concentrations were highest in the upper estuary in summer when freshwater discharge was low. In spring, PC:PN ratios were >13, indicating a strong influence by allochthonous plant detritus on PC and PN concentrations. However, high concentrations of PC and PN in fall coincided with maximum chlorophyll a concentrations and PC:PN ratios were <8, indicating in situ productivity controlled PC and PN levels. During late spring and summer, DIN concentrations decreased from >100 to <10 μg-at l^?1, resulting mainly from the nonconservative behavior of NO₃ ^?, which dominated the DIN pool. Atomic ratios of both the inorganic and total forms of N and P exceeded 100 in spring, but by summer, ratios decreased to <5 and <15, respectively. The seasonal and spatial changes in both absolute concentrations and ratios of N and P reflect the strong influence of allochthonous inputs on nutrient distributions in spring, followed by the effects of internal processes in summer and fall.     

On global forces of nature driving the Earth’s climate. Are humans involved?

The authors identify and describe the following global forces of nature driving the Earth’s climate: (1) solar radiation as a dominant external energy supplier to the Earth, (2) outgassing as a major supplier of gases to the World Ocean and the atmosphere, and, possibly, (3) microbial activities generating and consuming atmospheric gases at the interface of lithosphere and atmosphere. The writers provide quantitative estimates of the scope and extent of their corresponding effects on the Earth’s climate. Quantitative comparison of the scope and extent of the forces of nature and anthropogenic influences on the Earth’s climate is especially important at the time of broad-scale public debates on current global warming. The writers show that the human-induced climatic changes are negligible.     

Conditioning Geostatistical Operations to Nonlinear Volume Averages

The all-important process of data integration calls for algorithms that can handle secondary data often defined as nonlinear averages of the primary (hard) data over specific areas or volumes. It is suggested to approximate these nonlinear averages by linear averages of a nonlinear transform of the primary variable. Kriging of such nonlinear transforms, followed by the inverse transform, allows exact reproduction of all original data, both of point support and nonlinear volume averages. In a simulation mode, the previous cokriging provides the mean and variance of a conditional distribution from which to draw a simulated value, which is then backtransformed into a simulated value of the primary variable. The nonlinear averaged data values are then reproduced exactly. The direct sequential simulation algorithm adopted does not call for using any Gaussian distribution.     

A fabric-based sand plasticity model with reversal surfaces within anisotropic critical state theory

Acta Geotechnica - The paper describes the formulation and capabilities of a new constitutive model that accounts for the effects of fabric anisotropy on the response of granular materials under...     

Enzymatic microbial Mn(II) oxidation and Mn biooxide production in the Guaymas Basin deep-sea hydrothermal plume

Microorganisms play important roles in mediating biogeochemical reactions in deep-sea hydrothermal plumes, but little is known regarding the mechanisms that underpin these transformations. At Guaymas Basin (GB) in the Gulf of California, hydrothermal vents inject fluids laden with dissolved Mn(II) (dMn) into the deep waters of the basin where it is oxidized and precipitated as particulate Mn(III/IV) oxides, forming turbid hydrothermal “clouds”. Previous studies have predicted extremely short residence times for dMn at GB and suggested they are the result of microbially-mediated Mn(II) oxidation and precipitation. Here we present biogeochemical results that support a central role for microorganisms in driving Mn(II) oxidation in the GB hydrothermal plume, with enzymes being the primary catalytic agent. dMn removal rates at GB are remarkably fast for a deep-sea hydrothermal plume (up to 2 nM/h). These rapid rates were only observed within the plume, not in background deep-sea water above the GB plume or at GB plume depths (∼1750-2000 m) in the neighboring Carmen Basin, where there is no known venting. dMn removal is dramatically inhibited under anoxic conditions and by the presence of the biological poison, sodium azide. A conspicuous temperature optimum of dMn removal rates (∼40 °C) and a saturation-like (i.e. Michaelis-Menten) response to O₂ concentration were observed, indicating an enzymatic mechanism. dMn removal was resistant to heat treatment used to select for spore-forming organisms, but very sensitive to low concentrations of added Cu, a cofactor required by the putative Mn(II)-oxidizing enzyme. Extended X-ray absorption fine structure spectroscopy (EXAFS) and synchrotron radiation-based X-ray diffraction (SR-XRD) revealed the Mn oxides to have a hexagonal birnessite or δ-MnO₂-like mineral structure, indicating that these freshly formed deep-sea Mn oxides are strikingly similar to primary biogenic Mn oxides produced by laboratory cultures of bacteria. Overall, these results reveal a vigorous Mn biogeochemical cycle in the GB hydrothermal plume, where a distinct microbial community enzymatically catalyzes rapid Mn(II) oxidation and the production of Mn biooxides.     

Ultrapotassic Magmas along the Flanks of the Oligo-Miocene Rio Grande Rift, USA: Monitors of the Zone of Lithospheric Mantle Extension and Thinning Beneath a Continental Rift

Recent theoretical studies of rift tectonics have concludedthat their observed geophysical features, require that (1) extensionaffects a much wider zone of the underlying lithospheric mantlethan the crust; (2) early extension involves a comparativelywide zone that narrows with time. The Neogene evolution of thesegment of the Rio Grande rift between the Great Plains andColorado Plateau shows this theoretical pattern clearly. Thewidth of the crustal extension zone narrowed from {small tilde}170km in the Oligo-Miocene to {small tilde}50 km in the Pliocene.In contrast, both gravity and teleseismic studies indicate thatthe current width of the zone of thinned lithospheric mantle(ß = 2–3) beneath the rift is {small tilde}750km. To assess the contributions of lithosphere- and asthenosphere-derivedmelts to the magmatismassociated with the early phase of developmentof the Rio Grande rift, we have undertaken a 670-km geochemicaltraverse of Oligo-Miocene volcanism between latitudes 36 and38N. Our section is centered on the present-day axis of therift in the Espanola Basin. It extends from the Navajo volcanicfield, Arizona, to Two Buttes, SE Colorado, and intersects hypabyssalintrusions on the rift shoulders at Dulce, west of the rift,and Spanish Peaks to the east. We have sampled a diverse rangeof magma types that vary in composition from ultrapotassic toHy- and Ne-normative basalts. A geochemical profile along thistraverse shows a spatially symmetrical variation in elementand oxide ratios, such as Na₂O/K₂O and Ba/Nb, and also in Srand Nd isotope ratios. On the rift flanks and shoulders Oligo-Miocenevolcanism was dominated by K-rich mafic magmatism, whereas atthe rift axis tholeiitic and alkalic basalts with whole-rockcompositions similar to those of ocean-island basalts (OIB)were erupted. This symmetrical geochemical variation broadlyparallels the corresponding teleseismic lithosphere thicknessprofile and is a mirror image of the gravity profile. We interpret the OIB-type magmas at the rift axis as predominantlyasthenosphere-derived melts. These suggest that mantle upwelling,and melting by decompression, were occurring during the earlydevelopment of the Rio Grande rift The symmetrical variationof incompatible elements and isotope ratios in rocks about therift axis suggests that the sources of the K-rich mafic magmason the stable flanks and shoulders of the rift are not directlyrelated to the subduction of the Farallon plate: an asymmetricprocess. Instead, we propose that the K-rich mafic magmas onthe flanks and shoulders of the Rio Grande rift are derivedfrom the melting of a metasomatized layer in the lithosphericmantle during extension. *Present address: British Antarctic Survey, High Cross, Madingley Road, Cambridge CB3 0ET, UK     

Physico-chemical environment of pedogenic carbonate formation in Devonian vertic palaeosols, central Appalachians, USA

The morphology and geochemistry of pedogenic carbonate found in vertic claystone palaeosols in the Devonian Catskill Formation in central Pennsylvania preserve a record of the physical and chemical environment of carbonate precipitation. The carbonate is characterized by three distinct petrographic generations. Pedogenic rhizoliths and nodules are the earliest precipitated generation, and typically consist of dull red-brown luminescent micrite. Clear, equant calcite spar cement fills voids in the centres of rhizoliths, as well as circumgranular cracks and septarian voids in nodules. Early spar cements are non-luminescent to dull luminescent, whereas later spar cements exhibit bright yellow-orange luminescence. Late stage pedogenic fractures are always occluded with very bright yellow-orange luminescent spar cements. The incorporation of progressively higher concentrations of Mn (up to 34000 ppm) into successively younger calcite spar cements, without concomitant increases in Fe, suggests carbonate precipitation from an evolving meteoric water in which Mn²⁺ became increasingly mobile over time. The increased mobility is possibly due to decreasing Eh, resulting from oxidation of organic matter after rapid soil burial on the floodplain. The amount of Fe²⁺ available for incorporation into calcite was limited because most iron was immobile, having been earlier oxidized and bound to the palaeosol clay matrix as a poorly crystallized ferric oxide or oxyhydroxide mineral. Carbon isotope compositions of pedogenic carbonate correlate with the inferred depth of carbonate precipitation. Rhizoliths preserved below the lowest stratigraphic occurrences of pedogenic slickensides are consistently depleted in ¹³C relative to nodules, which formed stratigraphically higher, within the zone of active soil shrink and swell processes. Nodular carbonate, precipitated in proximity to deep cracks in the soil, is enriched due to increased gas exchange with isotopically heavy atmospheric CO₂. Accordingly, rhizolith compositions will most accurately estimate palaeoatmospheric levels of CO₂; the use of nodule compositions may result in overestimation of P_CO2 by as much as 30%.