Chemical evolution of the Mt. Hekla,Iceland, groundwaters: A natural analogue for CO2 sequestration in basaltic rocks

A detailed study of the chemical composition of the groundwater surrounding the Mt. Hekla volcano in south Iceland was performed to assess fluid evolution and toxic metal mobility during CO₂-rich fluid basalt interaction. These fluids provide a natural analogue for evaluating the consequences of CO₂ sequestration in basalt. The concentration of dissolved inorganic C in these groundwaters decreases from 3.88 to 0.746 mmol/kg with increasing basalt dissolution while the pH increases from 6.9 to 9.2. This observation provides direct evidence of the potential for basalt dissolution to sequester CO₂. Reaction path calculations suggest that dolomite and calcite precipitation is largely responsible for this drop in groundwater dissolved C concentration. The concentrations of toxic metal(loid)s in the waters are low, for example the maximum measured concentrations of Cd, As and Pb were 0.09, 22.8 and 0.06 nmol/kg, respectively. Reaction path modelling indicates that although many toxic metals may be initially liberated by the dissolution of basalt by acidic CO₂-rich solutions, these metals are reincorporated into solid phases as the groundwaters are neutralized by continued basalt dissolution. The identity of the secondary toxic metal bearing phases depends on the metal. For example, calculations suggest that Sr and Ba are incorporated into carbonates, while Pb, Zn and Cd are incorporated into Fe (oxy)hydroxide phases.     

Depositional environment of a Kimmeridgian carbonate 'black band' (Akkuyu Formation, south-western Turkey)

The Upper Jurassic Akkuyu Formation of south-western Turkey consists of pale-coloured carbonate facies, but includes a peculiar ‘black band’ at its base. In order to characterize the depositional environment of this level, a sedimentological, organic and inorganic geochemical study was performed on 30 samples. Three units are distinguished. Unit 1 consists of black marlstones, very rich in organic carbon (22–30%) with HI (hydrogen index) values around 600. The organic matter is an amorphous homogeneous material even at nanoscopic scale. This unit is also characterized by a very high concentration of V ( >1000 p.p.m.) and a δ¹³C_org value around ?26·5‰. Unit 2 shows thin-bedded black limestones with chert layers. Its organic content varies from 2% to 6%. As in unit 1, the HI values are uniformly high (600), and gas chromatography shows a high quantity of hopanes. The V concentration is also high (≈400 p.p.m.). The unit has a high Sr/Ca ratio, an organic carbon isotopic ratio close to ?28·7‰ and diffuse, nanoscopically amorphous organic material that is closely associated with pyrite. Unit 3 corresponds to the white limestones overlying the ‘black band’. This calcitic facies is almost devoid of organic carbon (<0·1%). The δ¹³C_org values are similar to those of unit 1 (?25·5‰ to ?26‰). Deposition occurred in a basinal environment surrounded by a carbonate platform. Primary productivity was high but not exceptional; terrestrial organic inputs were scarce. Bottom waters were probably euxinic during the deposition of unit 1. The presence of both hopane-rich and sulphur-rich nanoscopically amorphous organic matter may be the result of strong sulphate-reducing bacterial activity. Coupled with low amounts of iron, this led to intense vulcanization of the organic matter and thus good preservation. With the onset of unit 2 deposition, environmental conditions became less extreme, perhaps because of cooler water temperatures. Finally, the depositional conditions became oxic, leading to the accumulation of pale-coloured organic-poor limestones of unit 3.     

Geology of the epithermal Ag–Au Huevos Verdes vein system and San José district, Deseado massif, Patagonia, Argentina

The San José district is located in the northwest part of the Deseado massif and hosts a number of epithermal Ag–Au quartz veins of intermediate sulfidation style, including the Huevos Verdes vein system. Veins are hosted by andesitic rocks of the Bajo Pobre Formation and locally by rhyodacitic pyroclastic rocks of the Chon Aike Formation. New ⁴⁰Ar/³⁹Ar constraints on the age of host rocks and mineralization define Late Jurassic ages of 151.3 ± 0.7 Ma to 144.7 ± 0.1 Ma for volcanic rocks of the Bajo Pobre Formation and of 147.6 ± 1.1 Ma for the Chon Aike Formation. Illite ages of the Huevos Verdes vein system of 140.8 ± 0.2 and 140.5 ± 0.3 Ma are 4 m.y. younger than the volcanic host rock unit. These age dates are among the youngest reported for Jurassic volcanism in the Deseado massif and correlate well with the regional context of magmatic and hydrothermal activity. The Huevos Verdes vein system has a strike length of 2,000 m, with several ore shoots along strike. The vein consists of a pre-ore stage and three main ore stages. Early barren quartz and chalcedony are followed by a mottled quartz stage of coarse saccharoidal quartz with irregular streaks and discontinuous bands of sulfide-rich material. The banded quartz–sulfide stage consists of sulfide-rich bands alternating with bands of quartz and bands of chlorite ± illite. Late-stage sulfide-rich veinlets are associated with kaolinite gangue. Ore minerals are argentite and electrum, together with pyrite, sphalerite, galena, chalcopyrite, minor bornite, covellite, and ruby silver. Wall rock alteration is characterized by narrow (< 3 m) halos of illite and illite/smectite next to veins, grading outward into propylitic alteration. Gangue minerals are dominantly massive quartz intergrown with minor to accessory adularia. Epidote, illite, illite/smectite, and, preferentially at deeper levels, Fe-chlorite gangue indicate near-neutral pH hydrothermal fluids at temperatures of >220°C. Kaolinite occurring with the late sulfide-rich veinlet stage indicates pH < 4 and a temperature of <200°C. The Huevos Verdes system has an overall strike of 325°, dipping on average 65° NE. The orientations of individual ore shoots are controlled by vein strike and intersecting north-northwest-striking faults. We propose a structural model for the time of mineralization of the San José district, consisting of a conjugate shear pair of sinistral north-northwest- and dextral west-northwest-striking faults that correspond to R and R′ in the Riedel shear model and that are related to master faults (M) of north-northeast-strike. Veins of 315° strike can be interpreted as nearly pure extensional fractures (T). Variations in vein strike predict an induced sinistral shear component for strike directions of >315°, whereas strike directions of <315° are predicted with an induced dextral strike–slip movement. The components of the structural model appear to be present on a regional scale and are not restricted to the San José district.     

Low temperature volatile production at the Lost City Hydrothermal Field, evidence from a hydrogen stable isotope geothermometer

Although commonly utilized in continental geothermal work, the water-hydrogen and methane-hydrogen isotope geothermometers have been neglected in hydrothermal studies. Here we report δD-CH₄ and δD-H₂ values from high-temperature, black smoker-type hydrothermal vents and low-temperature carbonate-hosted samples from the recently discovered Lost City Hydrothermal Field. Methane deuterium content is uniform across the dataset at − 120 ± 12‰. Hydrogen δD values vary from − 420‰ to − 330‰ at high-temperature vents to − 700‰ to − 600‰ at Lost City. The application of several geothermometer equations to a suite of hydrothermal vent volatile samples reveals that predicted temperatures are similar to measured vent temperatures at high-temperature vents, and 20-60 °C higher than those measured at the Lost City vents. We conclude that the overestimation of temperature at Lost City reflects 1) that methane and hydrogen are produced by serpentinization at > 110 °C, and 2) that isotopic equilibrium at temperatures < 70 °C is mediated by microbial sulfate reduction. The successful application of hydrogen isotope geothermometers to low-temperature Lost City hydrothermal samples encourages its employment with low-temperature diffuse hydrothermal fluids.     

Upper mantle structure of the South American continent and neighboring oceans from surface wave tomography

We present a new three-dimensional SV-wave velocity model for the upper mantle beneath South America and the surrounding oceans, built from the waveform inversion of 5850 Rayleigh wave seismograms. The dense path coverage and the use of higher modes to supplement the fundamental mode of surface waves allow us to constrain seismic heterogeneities with horizontal wavelengths of a few hundred kilometres in the uppermost 400 km of the mantle.The large scale features of our tomographic model confirm previous results from global and regional tomographic studies (e.g. the depth extent of the high velocity cratonic roots down to about 200–250 km).Several new features are highlighted in our model. Down to 100 km depth, the high velocity lid beneath the Amazonian craton is separated in two parts associated with the Guyana and Guapore shields, suggesting that the rifting episode responsible for the formation of the Amazon basin has involved a significant part of the lithosphere. Along the Andean subduction belt, the structure of the high velocity anomaly associated with the sudbduction of the Nazca plate beneath the South American plate reflects the along-strike variation in dip of the subducting plate. Slow velocities are observed down to about 100 km and 150 km at the intersection of the Carnegie and Chile ridges with the continent and are likely to represent the thermal anomalies associated with the subducted ridges. These lowered velocities might correspond to zones of weakness in the subducted plate and may have led to the formation of “slab windows” developed through unzipping of the subducted ridges; these windows might accommodate a transfer of asthenospheric mantle from the Pacific to the Atlantic ocean. From 150 to 250 km depth, the subducting Nazca plate is associated with high seismic velocities between 5°S and 37°S. We find high seismic velocities beneath the Paraná basin down to about 200 km depth, underlain by a low velocity anomaly in the depth range 200–400 km located beneath the Ponta Grossa arc at the southern tip of the basin. This high velocity anomaly is located southward of a narrow S-wave low velocity structure observed between 200 and 500–600 km depth in body wave studies, but irresolvable with our long period datasets. Both anomalies point to a model in which several, possibly diachronous, plumes have risen to the surface to generate the Paraná large igneous province (LIP).     

Environmental Monitoring and Peat Assessment Using Multivariate Analysis of Regional-Scale Geochemical Data

A compositional multivariate approach was used to analyse regional-scale soil geochemical data obtained as part of the Tellus Project generated by the Geological Survey of Northern Ireland. The multi-element total concentration data presented comprise X-ray fluorescence (XRF) analyses of 6862 rural soil samples collected at 20-cm depth on a non-aligned grid at one site per \(2\,\hbox {km}^{2}\). Censored data were imputed using published detection limits. Each soil sample site was assigned to the regional geology map, resulting in spatial data for one categorical variable and 35 continuous variables comprised of individual and amalgamated elements. This paper examines the extent to which soil geochemistry reflects the underlying geology or superficial deposits. Since the soil geochemistry is compositional, log-ratios were computed to adequately evaluate the data using multivariate statistical methods. Principal component analysis (PCA) and minimum/maximum autocorrelation factors (MAF) were used to carry out linear discriminant analysis (LDA) as a means to discover and validate processes related to the geologic assemblages coded as age bracket. Peat cover was introduced as an additional category to measure the ability to predict and monitor fragile ecosystems. Overall prediction accuracies for the age bracket categories were 68.4 % using PCA and 74.7 % using MAF. With inclusion of peat, the accuracy for LDA classification decreased to 65.0 and 69.9 %, respectively. The increase in misclassification due to the presence of peat may reflect degradation of peat-covered areas since the creation of superficial deposit classification.     

Modeling the 2D behavior of dry‐stone retaining walls by a fully discrete element method

The dry‐stone retaining walls (DSRW) have been tipped as a promising solution for sustainable development. However, before recently, their behavior is relatively obscure. In this study, discrete element method (DEM) approach was applied to simulate the plane strain failure of these walls. A commercial DEM package (PFC2D™) was used throughout this study. The authors used a fully discrete approach; thus, both the wall and the backfill were modeled as discrete elements. The methodology for obtaining the micromechanical parameters was discussed in detail; this includes the three mechanical sub‐systems of DSRWs: wall, backfill and interface. The models were loaded progressively until failure, and then the results were compared with the full‐scale experimental results where the walls were loaded, respectively, with hydrostatic load and backfill. Despite its complexity and its intensive calculation time, DEM model can then be used to validate a more simplified approach. Copyright © 2015 John Wiley & Sons, Ltd.