Chronology building using objective identification of annual signals in trace element profiles of stalagmites

Determination of annual lamination provides important additional constraints to radiometric dates on speleothems, both for dating the duration of specific growth intervals and optimizing growth models. In the absence of visible laminae, however, speleothem age models are reliant upon curve fitting through discretely dated points and are therefore inherently more uncertain than annual chronologies from laminae. Given that the impact of seasonality on speleothems is expected to be strong enough to generate an annual pulse in trace element chemistry regardless of whether or not visible or fluorescent growth laminae are visible, we demonstrate the potential for deriving high-resolution stalagmite chronologies from non-laminated samples using annual chemical variations in stalagmites from two Alpine caves (Obir, Austria and Ernesto, NE Italy). Trace element data were obtained by ion microprobe analyses for H, P, Mg, Na, Sr and Ba and the annual signal was sought using spectral and wavelet analysis. An automated chemical peak-counting software tool was developed in MATLAB^©. It counts significant annual peaks using criteria of minimum amplitude in relation to the local standard deviation of signal variation and minimum separation between peaks determined by the thickness of the preceding layers. Verification of the tool using visibly laminated samples suggests the software is a reliable and accurate method of chronology building, with hit ratios greater than 0.93 and less than 0.75% false alarm occurrences. Used in conjunction with other dating methods such as radiocarbon, U–Th and sulphur peak dating, the automated chemical laminae chronology-building approach provides a more meaningful alternative to simple age-depth curve fitting for non-laminated samples.     

Evaluation of cosmogenic 3He and 21Ne production rates in olivine and pyroxene from two Pleistocene basalt flows,western Grand Canyon,AZ, USA

Combining cosmogenic ³He and ²¹Ne (³He_c and ²¹Ne_c) measurements on both pyroxene and olivine from the Pleistocene Bar Ten flows (85–107 ka) greatly increases our ability to evaluate the accuracy of ³He_c and ²¹Ne_c production rates and, therefore, ³He_c and ²¹Ne_c surface exposure ages. Comparison of ³He_c and ²¹Ne_c age-pairs yielded by experimentally determined production rates and composition-based model calculations indicates that the former give more accurate surface exposure ages than the latter in this study. However, experimental production rates should be adjusted to the composition of the minerals being analyzed to obtain the best agreement between ³He_c and ²¹Ne_c ages for any given sample. ²¹Ne_c/³He_c values are 0.400 ± 0.029 and 0.204 ± 0.014 for olivine and pyroxene, respectively, in Bar Ten lava flows, in agreement with previously published values, and indicate that ²¹Ne_c/³He_c in olivine and pyroxene is not affected by erosion and remains constant with latitude, elevation, and time (up to 10 Myr). Samples with ²¹Ne_c/³He_c that do not agree with these values may indicate the presence of non-cosmogenic helium and/or neon. The neon three-isotope diagram can also indicate whether or not all excess neon in mineral separates comes from cosmogenic sources. An error-weighted regression for olivine defines a spallation line [y = (1.033 ± 0.031)x + (0.09876 ± 0.00033)], which is indistinguishable from that for pyroxene (Schäfer et al., 1999). We have derived a production rate of 25 ± 8 at/g/yr for ²¹Ne_c in clinopyroxene (En_43–44) based on the ⁴⁰Ar/³⁹Ar age of the upper Bar Ten flow. Our study indicates that the production rate of ²¹Ne_c in olivine may be slightly higher than previously determined. Cosmogenic ³He and ²¹Ne remain extremely useful, particularly when paired, in determining accurate eruption ages of young olivine- and pyroxene-rich basaltic lava flows.     

Multistage Variscan magmatism in the central Tauern Window (Austria) unveiled by U/Pb SHRIMP zircon data

U/Pb SHRIMP ages of nine Variscan leucocratic orthogneisses from the central Tauern Window (Austria) reveal three distinct pulses of magmatism in Early Carboniferous (Visean), Late Carboniferous (Stephanian) and Early Permian, each involving granitoid intrusions and a contemporaneous opening of volcano-sedimentary basins. A similar relationship has been reported for the Carboniferous parts of the basement of the Alps further to the west, e.g. the “External massifs” in Switzerland. After the intrusion of subduction-related, volcanic-arc granitoids (374?±?10?Ma; Zwölferkogel gneiss), collisional intrusive-granitic, anatectic and extrusive-rhyolitic/dacitic rocks were produced over a short interval at ca. 340?Ma (Augengneiss of Felbertauern: 340?±?4?Ma, Hochweißenfeld gneiss: 342?± 5?Ma, Falkenbachlappen gneiss: 343?±?6?Ma). This Early Carboniferous magmatism, which produced relatively small volumes of melt, can be attributed to the amalgamation of the Gondwana-derived “Tauern Window” terrane with Laurussia–Avalonia. Probably due to the oblique nature of the collision, transtensional phenomena (i.e. volcano-sedimentary troughs and high-level intrusives) and transpressional regimes (i.e. regional metamorphism and stacked nappes with anatexis next to thrust planes) evolved contemporaneously. The magmas are mainly of the high-K I-type and may have been generated during a short phase of decompressional melting of lithospheric mantle and lower crustal sources. In the Late Carboniferous, a second pulse of magmatism occurred, producing batholiths of calc-alkaline I-type granitoids (e.g. Venediger tonalite: 296?±?4?Ma) and minor coeval bodies of felsic and intermediate volcanics (Heuschartenkopf gneiss: 299?±?4?Ma, Peitingalm gneiss: 300?±?5?Ma). Prior to this magmatism, several kilometres of upper crust must have been eroded, because volcano-sedimentary sequences hosting the Heu- schartenkopf and Peitingalm gneisses rest unconformably on 340-Ma-old granitoids. The youngest (Permian) period of magma generation contains the intrusion of the S-type Granatspitz Central Gneiss at 271?±?4?Ma and the extrusion of the rhyolitic Schönbachwald gneiss protolith at 279?±?9?Ma. These magmatic rocks may have been associated with local extension along continental wrench zones through the Variscan orogenic crust or with a Permian rifting event. The Permian and the above-mentioned Late Carboniferous volcano-sedimentary sequences were probably deposited in intra-continental graben structures, which survived post-Variscan uplift and Alpine compressional tectonics.     

U-series evidence for crustal involvement and magma residence times in the petrogenesis of Parinacota volcano, Chile

In this study, we present Th–U disequilibria as well as radiogenic and trace element data for recent volcanic rocks from the Nevados de Payachata volcano which erupted through ∼70 km of continental crust in the Central Volcanic Zone of the Andes (18°S, 69°W). Both lavas and mineral separates were analyzed by mass spectrometry for ²³⁸U–²³⁰Th disequilibria. The lavas are characterized either by ²³⁰Th enrichment or depletion relative to its parent nuclide ²³⁸U. Mineral separates are used to derive U–Th isochron ages and these ages compare favorably with inferred stratigraphic ages or K–Ar ages, although in one case the U–Th age is significantly older than the stratigraphic age. Despite relatively constant Sr, Nd, and Pb isotope ratios, the lavas display inverse trends in ²³⁰Th/²³⁸U versus Ce/Yb or Ba/Hf diagrams. These trends cannot be interpreted by simple two-component mixing. Rather, there must be three (and perhaps four components) involved in the genesis of the Parinacota lavas. A mantle wedge, a slab fluid, and a lower crustal component can be identified. A sediment component is more difficult to detect as it is difficult to decipher its signature because of the strong crustal influence. The existence of binary arrays can be explained by variable amounts of crustal material. The process of crust–mantle interaction must have been short enough to preserve U–Th disequilibrium (<300 ka). Received: 21 April 1999 / Accepted: 11 March 2000     

Lippmann Diagrams: Theory and Application to Carbonate Systems

Since 1980 when F. Lippmann's seminal paper appeared, ourunderstanding of solubility equilibria involving ionic solidsolutions has been advanced by theoretical considerations as wellas careful experimental studies designed to determine excess Gibbsfunctions. A unified theory of solid-solution aqueous-solutionequilibria as well as the thermodynamic background of thephenomenon of ``stoichiometric saturation' are reviewed.It is shown that Lippmann diagrams effectively summarize thethermodynamic basis of solid-solute aqueous-solution equilibria ofsparingly soluble metal carbonate systems. Clearly, the predictivepower of these diagrams may be limited due to kineticrestrictions. Only when dissolution and precipitation areessentially reversible, favourable conditions to synthesizehomogeneous solid phases can be derived from studies of equilibria.     

Some modifications of Stokes' formula that account for truncation and potential coefficient errors

 Stokes' formula from 1849 is still the basis for the gravimetric determination of the geoid. The modification of the formula, originating with Molodensky, aims at reducing the truncation error outside a spherical cap of integration. This goal is still prevalent among various modifications. In contrast to these approaches, some least-squares types of modification that aim at reducing the truncation error, as well as the error stemming from the potential coefficients, are demonstrated. The least-squares estimators are provided in the two cases that (1) Stokes' kernel is a priori modified (e.g. according to Molodensky's approach) and (2) Stokes' kernel is optimally modified to minimize the global mean square error. Meissl-type modifications are also studied. In addition, the use of a higher than second-degree reference field versus the original (Pizzetti-type) reference field is discussed, and it is concluded that the former choice of reference field implies increased computer labour to achieve the same result as with the original reference field. Received: 14 December 1998 / Accepted: 4 October 1999     

Quartz Cement in Middle Jurassic Reservoir Sandstones in North Sea A Review. Part II： Duration and Silica Sources

The timing and duration of quartz cementation in sandstones have been mainly inferred from diagenetic texture, relationship between pore filling minerals, fluid inclusions and isotopic data. Fluid inclusion temperatures from North Sea reservoir sandstones indicate that most of the quartz cement forms at temperature exceeding 90℃ and is continually proceeding after oil emplacement, based on the fluid inclusion temperatures in quartz overgrowth which is approaching the bottom-hole temperatures. The duration of quartz cement after oil emplacement depends upon the saturation of porewater and the distribution of pore water film and the property of water-wet or oil-wet of the reactants. The leaching of K-feldspar by meteoric water requires pore water flow to move the released potassium and sodium and silica out the solution, which suggests the mechanism does not appear to be a major source of silica for quartz cementation. The quartz cementation coincidence with the compaction and pressure solution suggests the major source of silica. The alteration of feldspar by illitization of kaolinite may serve as another important source of silica at deep burial depth. External sources are not need to call on for illustrating the quartz cementation, because there is no evidences for large scale convection of pore water flow occurred in the burial history of reservoir sandstones of middle Jurassic in the North Sea.     

Analysis of the positive ionospheric response to a moderate geomagnetic storm using a global numerical model

Current theories of F-layer storms are discussed using numerical simulations with the Upper Atmosphere Model, a global self-consistent, time dependent numerical model of the thermosphere-ionosphere-plasmasphere-magnetosphere system including electrodynamical coupling effects. A case study of a moderate geomagnetic storm at low solar activity during the northern winter solstice exemplifies the complex storm phenomena. The study focuses on positive ionospheric storm effects in relation to thermospheric disturbances in general and thermospheric composition changes in particular. It investigates the dynamical effects of both neutral meridional winds and electric fields caused by the disturbance dynamo effect. The penetration of short-time electric fields of magnetospheric origin during storm intensification phases is shown for the first time in this model study. Comparisons of the calculated thermospheric composition changes with satellite observations of AE-C and ESRO-4 during storm time show a good agreement. The empirical MSISE90 model, however, is less consistent with the simulations. It does not show the equatorward propagation of the disturbances and predicts that they have a gentler latitudinal gradient. Both theoretical and experimental data reveal that although the ratio of [O]/[N₂] at high latitudes decreases significantly during the magnetic storm compared with the quiet time level, at mid to low latitudes it does not increase (at fixed altitudes) above the quiet reference level. Meanwhile, the ionospheric storm is positive there. We conclude that the positive phase of the ionospheric storm is mainly due to uplifting of ionospheric F2-region plasma at mid latitudes and its equatorward movement at low latitudes along geomagnetic field lines caused by large-scale neutral wind circulation and the passage of travelling atmospheric disturbances (TADs). The calculated zonal electric field disturbances also help to create the positive ionospheric disturbances both at middle and low latitudes. Minor contributions arise from the general density enhancement of all constituents during geomagnetic storms, which favours ion production processes above ion losses at fixed height under day-light conditions.     

Morphology of NmF2 nighttime increases in the Eurasian sector

A statistical analysis of two peaks (pre-midnight and post-midnight) occurrence in NmF2 daily variations was made on a latitudinal chain of four ionosonde stations in the Eurasian longitudinal sector. Overall 6182 cases of the first and 5600 cases of the second peak occurrence were analyzed using all available foF2 observations for the years of solar maximum and minimum. Well-pronounced and systematic variations with season and solar activity were revealed in the occurrence probability of the peaks, their amplitude and timing. The pattern of both peaks occurrence is similar during winter and equinoxes for midlatitude stations implying one and the same mechanism of their formation. The pre-midnight summer peak shows specific variations in particular during solar maximum pointing to a different mechanism controlling its appearance. Possible mechanisms of both peaks formation are discussed.