Middle Eocene to Early Miocene sedimentary evolution of the western Lombardian segment of the South Alpine foredeep (Italy)

The main steps of the sedimentary evolution of the west Lombardian South Alpine foredeep between the Eocene and the Early Miocene are described. The oldest is a Bartonian carbonate decrease in hemipelagic sediments linked with an increase in terrigenous input, possibly related to a rainfall increase in the Alps. Between the Middle Eocene and the early Chattian, a volcanoclastic input is associated with an extensional tectonic regime, coeval with magma emplacement in the southern-central Alps, and with volcanogenic deposits of the European foredeep and Apennines, suggesting a regional extensional tectonic phase leading to the ascent of magma. During Late Eocene to Early Oligocene, two periods of coarse clastic sedimentation occurred, probably controlled by eustasy. The first, during Late Eocene, fed by a local South Alpine source, the second, earliest Oligocene in age, supplied by the Central Alps. In the Chattian, a strong increase in coarse supply records the massive erosion of Central Alps, coupled with a structures growth phase in the subsurface; it was followed by an Aquitanian rearrangement of the Alpine drainage systems suggested by both petrography of clastic sediments and retreat of depositional systems, while subsurface sheet-like geometry of Aquitanian turbidites marks a strong decrease in tectonic activity.     

The Valanginian carbon isotope event: a first episode of greenhouse climate conditions during the Cretaceous

Lower Cretaceous pelagic carbonates outcropping along the Southern Alps of northern Italy provide a record of Tethyan palaeoceanography as well as of low frequency fluctuations in the global carbon cycle. The carbonate C-isotope stratigraphy established at five selected localities in the Southern Alps allows an accurate picture to be drawn of the duration and amplitude of the Valanginian C-isotope event. δ¹³C values near 1.25–1.50% determined in Berriasian and lower Valanginian sediments are replaced by more pdsitive δ¹³C values near 3% in the late Valanginian. The carbonate C-isotope excursion ends in the early Hauterivian with values fluctuating between 1.5% and 2%. The carbonate C-isotope excursion is accompanied by a positive excursion in the total organic carbon C-isotope curve. The Valanginian C-isotope excursion identified in Tethyan sediments correlates with a C-isotope excursion recorded in the western North Atlantic, in the Gulf of Mexico, and in the Central Pacific (DSDP Sites 534,391,535 and 167). By analogy with the Aptian stage, also marked by a significant positive C-isotope excursion, the time of positive δ¹³C values is regarded as a time of accelerated carbon cycling coupled with increased burial rates of organic carbon and detrital material in oceanic sediments. A warm and humid climate, possiblycoupled with a high atmospheric CO₂ content and a high global sea-level, may have triggered the acceleration of the global carbon cycling. In this case the Valanginian C-isotope event would reflect a first episode of Greenhouse Earth conditions during the Cretaceous.     

Snow and climate trends and their impact on seasonal runoff and hydrological drought types in selected mountain catchments in Central Europe

ABSTRACT

This study investigates changes in seasonal runoff and low flows related to changes in snow and climate variables in mountainous catchments in Central Europe. The period 1966–2012 was used to assess trends in climate and streamflow characteristics using a modified Mann–Kendall test. Droughts were classified into nine classes according to key snow and climate drivers. The results showed an increase in air temperature, decrease in snowfall fraction and snow depth, and changes in precipitation. This resulted in increased winter runoff and decreased late spring runoff due to earlier snowmelt, especially at elevations from 1000 to 1500 m a.s.l. Most of the hydrological droughts were connected to either low air temperatures and precipitation during winter or high winter air temperatures which caused below-average snow storages. Our findings show that, besides precipitation and air temperature, snow plays an important role in summer streamflow and drought occurrence in selected mountainous catchments.     

The chemical and hydrologic structure of Poa´s Volcano, Costa Rica

Comparison of the chemical characteristics of spring and river water draining the flanks of Poa´s Volcano, Costa Rica indicates that acid chloride sulfate springs of the northwestern flank of the volcano are derived by leakage and mixing of acid brines formed in the summit hydrothermal system with dilute flank groundwater. Acid chloride sulfate waters of the Rio Agrio drainage basin on the northwestern flank are the only waters on Poa´s that are affected by leakage of acid brines from the summit hydrothermal system. Acid sulfate waters found on the northwestern flank are produced by the interaction of surface and shallow groundwater with dry and wet acid deposition of SO₂ and H₂SO₄ aerosols, respectively. The acid deposition is caused by a plume of acid gases that is released by a shallow magma body located beneath the active crater of Poa´s.No evidence for a deep reservoir of neutral pH sodium chloride brine is found at Poa´s. The lack of discharge of sodium chloride waters at Poa´s is attributed to two factors: (1) the presence of a relatively volatile-rich magma body degassing at shallow depths (< 1 km) into a high level summit groundwater system; and (2) the hydrologic structure of the volcano in which high rates of recharge combine with rapid lateral flow of shallow groundwater to prevent deep-seated sodium chloride fluids from ascending to the surface. The shallow depth of the volatile-rich magma results in the degassing of large quantities of SO₂ and HCl. These gases are readily hydrolyzed and quickly mix with meteoric water to form a reservoir of acid chloride-sulfate brine in the summit hydrothermal system. High recharge rates and steep hydraulic gradients associated with elevated topographic features of the summit region promote lateral flow of acid brines generated in the summit hydrothermal system. However, the same high recharge rates and steep hydraulic gradients prevent lateral flow of deep-seated fluids, thereby masking the presence of any sodium chloride brines that may exist in deeper parts of the volcanic edifice.Structural, stratigraphic, and topographic features of Poa´s Volcano are critical in restricting flow of acid brines to the northwestern flank of the volcano. A permeable lava-lahar sequence that outcrops in the Rio Agrio drainage basin forms a hydraulic conduit between the crater lake and acid chloride sulfate springs. Spring water residence times are estimated from tritium data and indicate that flow of acid brines from the active crater to the Rio Agrio source springs is relatively rapid (3 to 17 years). Hydraulic conductivity values of the lava-lahar sequence calculated from residence time estimates range from 10⁻⁵ to 10⁻⁷ m/s. These values are consistent with hydraulic conductivity values determined by aquifer tests of fractured and porous lava/pyroclastic sequences at the base of the northwestern flank of the volcano.Fluxes of dissolved rock-forming elements in Rio Agrio indicate that approximately 4300 and 1650 m³ of rock are removed annually from the northwest flank aquifer and the active crater hydrothermal system, respectively. Over the lifetime of the hydrothermal system (100's to 1000's of years), significant increases in aquifer porosity and permeability should occur, in marked contrast to the reduction in permeability that often accompanies hydrothermal alteration in less acidic systems. Average fluxes of fluoride, chloride and sulfur calculated from discharge and compositional data collected in the Rio Agrio drainage basin over the period 1988–1990 are approximately 2, 38 and 30 metric tons/day. These fluxes should be representative of minimum volatile release rates at Poa´s in the last 10 to 20 years.     

Modeling ferrous-ferric iron chemistry with application to martian surface geochemistry

The Mars Global Surveyor, Mars Exploration Rover, and Mars Express missions have stimulated considerable thinking about the surficial geochemical evolution of Mars. Among the major recent mission findings are the presence of jarosite (a ferric sulfate salt), which requires formation from an acid-sulfate brine, and the occurrence of hematite and goethite on Mars. Recent ferric iron models have largely focused on 25 °C, which is a major limitation for models exploring the geochemical history of cold bodies such as Mars. Until recently, our work on low-temperature iron-bearing brines involved ferrous but not ferric iron, also obviously a limitation. The objectives of this work were to (1) add ferric iron chemistry to an existing ferrous iron model (FREZCHEM), (2) extend this ferrous/ferric iron geochemical model to lower temperatures (<0 °C), and (3) use the reformulated model to explore ferrous/ferric iron chemistries on Mars.The FREZCHEM model is an equilibrium chemical thermodynamic model parameterized for concentrated electrolyte solutions using the Pitzer approach for the temperature range from <−70 to 25 °C and the pressure range from 1 to 1000 bars. Ferric chloride and sulfate mineral parameterizations were based, in part, on experimental data. Ferric oxide/hydroxide mineral parameterizations were based exclusively on Gibbs free energy and enthalpy data. New iron parameterizations added 23 new ferrous/ferric minerals to the model for this Na-K-Mg-Ca-Fe(II)-Fe(III)-H-Cl-SO₄-NO₃-OH-HCO₃-CO₃-CO₂-O₂-CH₄-H₂O system.The model was used to develop paragenetic sequences for Rio Tinto waters on Earth and a hypothetical Martian brine derived from acid weathering of basaltic minerals. In general, model simulations were in agreement with field evidence on Earth and Mars in predicting precipitation of stable iron minerals such as jarosites, goethite, and hematite. In addition, paragenetic simulations for Mars suggest that other iron minerals such as lepidocrocite, schwertmannite, ferricopiapite, copiapite, and bilinite may also be present on the surface of Mars. Evaporation or freezing of the Martian brine led to similar mineral precipitates. However, in freezing, compared to evaporation, the following key differences were found: (1) magnesium sulfates had higher hydration states; (2) there was greater total aqueous sulfate (SO_4T = SO₄ + HSO₄) removal; and (3) there was a significantly higher aqueous Cl/SO_4T ratio in the residual Na-Mg-Cl brine. Given the similarities of model results to observations, alternating dry/wet and freeze/thaw cycles and brine migration could have played major roles in vug formation, Cl stratification, and hematite concretion formation on Mars.