Did Paleogene North Atlantic rift-related eruptions drive early Eocene climate cooling?

The delivery of volcanogenic sulphur into the upper atmosphere by explosive eruptions is known to cause significant temporary climate cooling. Therefore, phreatomagmatic and phreatoplinian eruptions occurring during the final rifting stages of active flood basalt provinces provide a potent mechanism for triggering climate change.

During the early Eocene, the northeast Atlantic margin was subjected to repeated ashfall for 0.5 m.y. This was the result of extensive phreatomagmatic activity along 3000 km of the opening northeast Atlantic rift. These widespread, predominantly basaltic ashes are now preserved in marine sediments of the Balder Formation and its equivalents, and occur over an area extending from the Faroe Islands to Denmark and southern England. These ash-bearing sediments also contain pollen and spore floras derived from low diversity forests that grew in cooler, drier climates than were experienced either before or after these highly explosive eruptions. In addition, coeval plant macrofossil evidence from the Bighorn Basin, Wyoming, USA, also shows a comparable pattern of vegetation change. The coincidence of the ashes and cooler climate pollen and spore floras in northwest Europe identifies volcanism as the primary cause of climate cooling. Estimates show that whilst relatively few phreatomagmatic eruptive centres along the 3000 km opening rift system could readily generate 0.5–1 °C cooling, on an annual basis, only persistent or repeated volcanic phases would have been able to achieve the long-term cooling effect observed in the floral record. We propose that the cumulative effect of repeated Balder Formation eruptions initiated a biodiversity crisis in the northeast Atlantic margin forests. Only the decline of this persistent volcanic activity, and the subsequent climatic warming at the start of the Eocene Thermal Maximum allowed the growth of subtropical forests to develop across the region.     

Electronic structures of iron(III) and manganese(IV) (hydr)oxide minerals: Thermodynamics of photochemical reductive dissolution in aquatic environments

Sunlight-induced reduction and dissolution of colloidal Fe-Mn (hydr)oxide minerals yields elevated concentrations of Fe²⁺ and Mn²⁺ in natural waters. Since these elements may be biolimiting micronutrients, photochemical reactions might play a significant role in biogeochemical cycles. Reductive photodissolution of Fe (hydr)oxide minerals may also release sorbed metals. The reactivity of Fe-Mn (hydr)oxide minerals to sunlight-induced photochemical dissolution is determined by the electronic structure of the mineral-water interface. In this work, oxygen K-edge absorption and emission spectra were used to determine the electronic structures of iron(III) (hydr)oxides (hematite, goethite, lepidocrocite, akaganeite and schwertmannite) and manganese(IV) oxides (pyrolusite, birnessite, cryptomelane). The band gaps in the iron(III) (hydr)oxide minerals are near 2.0-2.5 eV; the band gaps in the manganese (IV) oxide phases are 1.0-1.8 eV. Using published values for the electrochemical flat-band potential for hematite together with experimental pH_pzc values for the (hydr)oxides, it is possible to predict the electrochemical potentials of the conduction and valence bands in aqueous solutions as a function of pH. The band potentials enable semiquantitative predictions of the susceptibilities of these minerals to photochemical dissolution in aqueous solutions. At pH 2 (e.g., acid-mine waters), photoreduction of iron(III) (hydr)oxides could yield millimolal concentrations of aqueous Fe²⁺ (assuming surface detachment of Fe²⁺ is not rate limiting). In seawater (pH 8.3), however, the direct photo-reduction of colloidal iron(III) (hydr)oxides to give nanomolal concentrations of dissolved, uncomplexed, Fe²⁺ is not thermodynamically feasible. This supports the hypothesis that the apparent photodissolution of iron(III) (hydr)oxides in marines systems results from Fe³⁺ reduction by photochemically produced superoxide. In contrast, the direct photoreduction of manganese oxides should be energetically feasible at pH 2 and 8.3.     

Source and movement of helium in the eastern Morongo groundwater Basin: The influence of regional tectonics on crustal and mantle helium fluxes

We assess the role of fracturing and seismicity on fluid-driven mass transport of helium using groundwaters from the eastern Morongo Basin (EMB), California, USA. The EMB, located ∼200 km east of Los Angeles, lies within a tectonically active region known as the Eastern California Shear Zone that exhibits both strike-slip and extensional deformation. Helium concentrations from 27 groundwaters range from 0.97 to 253.7 × 10⁻⁷ cm³ STP g⁻¹H₂O, with corresponding ³He/⁴He ratios falling between 1.0 and 0.26 R_A (where R_A is the ³He/⁴He ratio of air). All groundwaters had helium isotope ratios significantly higher than the crustal production value of ∼0.02 R_A. Dissolved helium concentrations were resolved into components associated with solubility equilibration, air entrainment, in situ production within the aquifer, and extraneous fluxes (both crustal and mantle derived). All samples contained a mantle helium-3 (³He_m) flux in the range of 4.5 to 1351 × 10⁻¹⁴ cm³ STP ³He cm⁻² yr⁻¹ and a crustal flux (J₀) between 0.03 and 300 × 10⁻⁷ cm³ STP ⁴He cm⁻² yr⁻¹. Groundwaters from the eastern part of the basin contained significantly higher ³He_m and deep crustal helium-4 (⁴He_dc) concentrations than other areas, suggesting a localized source for these components. ⁴He_dc and ³He_m are strongly correlated, and are associated with faults in the basin. A shallow thermal anomaly in a >3,000 m deep graben in the eastern basin suggests upflow of fluids through active faults associated with extensional tectonics. Regional tectonics appears to drive large scale crustal fluid transport, whereas episodic hydrofracturing provides an effective mechanism for mantle-crust volatile transport identified by variability in the magnitude of degassing fluxes (³He_m and J₀) across the basin.     

Evolution of a Holocene banner bank controlled by morphodynamics and structural setting of a macrotidal coast: Saint-Brieuc Bay(NW-Europe)

The morphology and internal structure of the Horaine Bank(Bay of Saint-Brieuc, NW France) are described based on multibeam echosounder and high-resolution seismic datasets coupled with vibro-core data. The Horaine Bank shows large-scale bedforms in the lee of a submerged rocky shoal, which allowed defining it as a Banner Bank.The internal structure of the sandbank reveals four seismic units(U1–U4) on a Cambrian basement(U0). The basal unit U1 is interpreted as reworked lowstand fluvial sediments those infilled micro incised valleys during a rise in sea level. This unit is overlain by paleo-coastal barrier sand-spit(U2) whose development was controlled by swell in the context of a rapid rise in sea level. The successive prograding unit(U3) is interpreted as flooding deposits in continuity with unit U2. The unit U4 is characterized by oblique reflectors oriented in two opposite directions. This last unit, dated post 3500 yr BP, corresponds to migrating dunes superimposed on the bank and observable in the high-resolution bathymetric data. The strong correlation between tidal currents and the apparent clockwise migration of dune crests suggests the presence of a tidal gyre controlling the present-day dynamics of most of the Horaine bank dunes. This study proposes a new model for the construction of banner banks characterized by the gradual transition of a sand spit to a banner bank during marine transgression and ensuing hydrodynamic variability.     

Variogram Model Selection via Nonparametric Derivative Estimation

Before optimal linear prediction can be performed on spatial data sets, the variogram is usually estimated at various lags and a parametric model is fitted to those estimates. Apart from possible a priori knowledge about the process and the user's subjectivity, there is no standard methodology for choosing among valid variogram models like the spherical or the exponential ones. This paper discusses the nonparametric estimation of the variogram and its derivative, based on the spectral representation of positive definite functions. The use of the estimated derivative to help choose among valid parametric variogram models is presented. Once a model is selected, its parameters can be estimated—for example, by generalized least squares. A small simulation study is performed that demonstrates the usefulness of estimating the derivative to help model selection and illustrates the issue of aliasing. MATLAB software for nonparametric variogram derivative estimation is available at http://www-math.mit.edu/~gorsich/derivative.html. An application to the Walker Lake data set is also presented.     

Nappe displacement in the Scandinavian Caledonides

Large areas of the Scandinavian Caledonides are eroded to the level of the basement/cover contact. Relationships between the Precambrian crystalline basement (largely Svecofennian-Dalslandian, 1800-1000 m.y.) and cover sequences are exposed both in transverse profiles through the mountain belt and along the belt in the various windows. These relationships provide an unique opportunity for studying the basement configuration, character of basement involvement and general nappe geometry. Major allochthonous units of the central part of the Scandinavian Caledonides — the Offerdal, Särv and Seve-Köli Nappe Complex — have been shown to wedge out westwards, having been displaced eastwards from environments along and west of the present Norwegian coast. Recent investigations have shown that these units (the Offerdal, Särv and Seve) reappear in western Norway as major pinch-and-swell structures, the lenses reaching thicknesses in the order of 2 km and with long axes of several tens of kilometres. Within the western parts of the Swedish Caledonides the thicker parts of the lenses approximately coincide with the axes of the late synforms which fold basement and cover together. Further west, in Norway, the tensing appears to be unrelated to the geometry of these major folds.This evidence increases estimates of nappe displacement distance (now thought to be in the order of at least 1000 km). At the same time it emphasizes that translation may account for only about half of this amount, the rest being achieved by stretching of the nappes. Apparently, a nappe sequence built up in the west which subsequently collapsed, leading to continued displacement eastwards on to the Baltoscandian Platform. Whereas basement shortening is of the order of several tens to perhaps hundreds of kilometres in the western part of the central Scandes, it is of lesser importance from central Trøndelag eastwards, a distance of about two hundred kilometres, to the Caledonian Front.Biostratigraphic evidence from the late-orogenic intramontane basins, taken in relation to the youngest units involved in the nappes, requires nappe translation into western Norway to have occurred after the Llandoverian (Köli Supergroup) and prior to the (Ludlovian?) Downtonian (Hitra Formation) deposition in the intramontane basins. The nappes contain sequences derived from a variety of probable oceanic and continental margin environments, and this translation may greatly exceed the minimum estimate of five hundred kilometres. Further displacement eastwards occurred during uplift of seaboard Norway and accompanied sedimentation both in the intra- and extramontane basins. The latter were not finally influenced by the décollement tectonics until after the Early Devonian.This evidence suggests that a compressive regime dominated the early phases of orogenesis during basement shortening, build up of the nappe pile and translation of these denser units on to the western margin of the Baltoscandian Platform. This compression subsequently gave way to a gravity regime, collapse and stretching of the nappes dominating the late phases of displacement on to the Baltoscandian Platform.     

Thermodynamic properties of almandine-grossular garnet solid solutions

The mixing properties of Fe₃Al₂Si₃O₁₂-Ca₃Al₂Si₃O₁₂ garnet solid solutions have been studied in the temperature range 850–1100° C. The experimental method involves measuring the composition of garnet in equilibrium with an assemblage in which the activity of the Ca₃Al₂Si₃O₁₂ component is fixed. Experiments on the assemblage garnet solid solution, anorthite, Al₂SiO₅ polymorph and quartz at known pressure and temperature fix the activity of the Ca₃Al₂Si₃O₁₂ component through the equilibrium: 1 $$\begin{gathered} {\text{3CaAl}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{8}} \rightleftarrows {\text{Ca}}_{\text{3}} {\text{Al}}_{\text{2}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} \hfill \\ {\text{Anorthite garnet}} \hfill \\ {\text{ + 2Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + SiO}}_{\text{2}} \hfill \\ {\text{ sillimanite/kyanite quartz}}{\text{.}} \hfill \\ \end{gathered}$$ This equilibrium, with either sillimanite or kyanite as the aluminosilicate mineral, was used to control \({\text{a}}_{{\text{Ca}}_{\text{3}} {\text{Al}}_{\text{2}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} }^{{\text{gt}}} \) . The compositions of the garnet solutions produced were determined by measurement of their unit cell edges. At 1 bar Fe₃Al₂Si₃O₁₂-Ca₃Al₂Si₃O₁₂ garnets exhibit negative deviations from ideality at the Fe-rich end of the series and positive deviations at the calcium end. With increasing pressure the activity coefficients for the Ca₃Al₂Si₃O₁₂ component increase because the partial molar volume of this component is greater than the molar volume of pure grossular. Previous studies indicate that the activity coefficients for the Ca₃Al₂Si₃O₁₂ component also increase with increasing (Mg/Mg+Fe) ratio of the garnet. The region of negative deviation from ideality implies a tendency towards formation of a stable Fe-Ca garnet component. Evidence in support of this conclusion has been found in a natural Fe-rich garnet which was found to contain two different garnet phases of distinctly different compositions.     

Diagenetic evolution of Aptian evaporites in the Namibe Basin (south‐west Angola)

The widespread and dissected nature of the Angolan gypsiferous salt residuals offers a uniquely detailed view of the lateral and vertical relations inherent to secondary evaporite textures, which typify exhumed salt masses worldwide. Such secondary textures are sometimes misinterpreted as primary evaporite textures. Thin, metre‐scale and patchy, dome‐like gypsum accumulations are well‐exposed within strongly incised present‐day river valleys along the eastern margin of the Namibe and Benguela basins (south‐west Angola). These sections are time equivalent to the main basinward subsurface evaporites (Aptian Loeme Formation) which mostly consist of halite. The gypsum (here called the Bambata Formation) is interpreted to represent the final residual product of fractional dissolution and recrystallization of the halite mass that occurred during Late Cretaceous margin uplift and continues today. This halite underwent multiple episodes of diagenetic alteration between its deposition and its final exhumation, leading to the formation of various secondary gypsum fabrics and solution‐related karst and breccia textures that typify the current evaporite outcrop. Four different diagenetic gypsum fabrics are defined: thinly bedded alabastrine, nodular alabastrine, displacive selenite rosettes and fibrous satin‐spar gypsum. Current arid conditions are responsible for a thin weathered crust developed at the top of the outcropping gypsum, but the fabrics in the main core of the current at‐surface evaporite unit mostly formed during the telogenetic stage of uplift prior to complete subaerial exposure. Alteration occurred as various dissolving and rehydrating saline minerals encountered shallow aquifers in the active phreatic and vadose zones. Geomorphological and petrographic analyses, mostly based on the cross‐cutting relations and crystallographic patterns in the outcrop, are used to propose a sequence of formation of these different fabrics.