Hydrochemistry of carbonate terrains in alpine glacial settings

Nearly 200 analyses of meltwaters, ice and snow from three alpine glacial sites in carbonate terrain are summarized and discussed in terms of sources of solutes and kinetic controls on the progress of weathering reactions. Most data derive from the Swiss Glacier de Tsanfleuron which is based on Cretaceous and Tertiary pure and impure limestones. Two other sites (Marmolada, Italian Dolomites and the Saskatchewan Glacier, Alberta) are based on a mixed calcitic-dolomitic substrate. Most solutes originate from carbonate dissolution; moreover, where pyrite is present its oxidation supplies significant sulphate and forces more dissolution of carbonate. The ratios Sr²⁺/Ca²⁺ and Mg²⁺/Ca²⁺ are much higher in Tsanfleuron melt-waters than local bedrock, a phenomenon that can be reproduced in the laboratory at small percentages of dissolution. These anomalous ratios are attributed to incongruent dissolution of traces of the metastable carbonates Mg-calcite and aragonite. These phases also provide Na⁺ to solution. K⁺ is argued to originate mainly by ion-exchange on clays with solute Ca²⁺. Quartz and very minor feldspar dissolution are also inferred. Locally enhanced input from atmospheric sources is recognized by high Cl^? and associated Na⁺. The progress of weathering reactions has been evaluated by the trends in the data, computer modelling and some simple laboratory experiments. The most dilute samples show a trend towards removal of CO₂ to low partial pressures (c. 10^?5.5 atmospheres), reflecting initially rapid carbonate dissolution and relatively slow dissolution of gaseous CO₂. Later addition of atmospheric CO₂ or acid from pyrite oxidation allows further carbonate dissolution, but solutions show a wide range of saturations, and CO₂ pressures as high as 10^?2.2 where pyrite oxidation is important. In a carbonate terrain, measurement of electroconductivity (corrected to 25°C) and alkalinity in the field allows the following preliminary deductions (where meq stands for milliequivalents): where S is the minimum meq(Ca²⁺ + Mg²⁺) produced by simple dissolution of carbonate unconnected with pyrite oxidation. As with any proxy method, these deductions do not remove the need for chemical analysis of waters in a given study area.     

The solubility of nantokite (CuCl(s)) and Cu speciation in low-density fluids near the critical isochore: An in-situ XAS study

The solubility of nantokite (CuCl_(s)) and the structure of the predominant copper species in supercritical water (290-400 bar at 420 °C; 350-450 °C at 290 bar; 500 °C at 350 bar; density = 0.14-0.65 g/cm³) were investigated concurrently using synchrotron X-ray absorption spectroscopy (XAS) techniques. These conditions were chosen as they represent single phase solutions near the critical isochore, where the fluid density is intermediate of typical values for vapour and brine and is highly sensitive to even small changes in pressure. X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption spectroscopy (EXAFS) analyses show that aqueous copper occurs in a slightly distorted linear coordination in the solutions studied, with an average of 1.35(±0.3) Cl and 0.65(±0.3) O neighbours. The solubility of CuCl_(s) decreases exponentially with decreasing water density (i.e., decreasing pressure at constant temperature), in a manner similar to the solubility behaviour of salts such as NaCl in water vapour. Based on this similarity, an apparent equilibrium constant for the dissolution reaction of 0.5 ± 0.4 was calculated from a regression of the data at 420 °C, and it was determined that each Cu atom is solvated by approximately three water molecules. This indicates that under these conditions, copper solubility is controlled mainly by the structure of the second-shell hydration, which is essentially invisible to the XAS techniques used in this study.These results demonstrate that for a supercritical fluid near the critical isochore, decreasing pressure may initiate precipitation of copper even before boiling or phase separation. Such a process could be responsible for near-surface ore deposition in seafloor hydrothermal systems, where supercritical fluids experience rapid pressure changes during the transition between lithostatic and hydrostatic domains.     

The Holocene volcanic history of Gran Canaria island: implications for volcanic hazards

Previous published data, combined with our results of 13 new radiocarbon ages and extensive geological fieldwork, indicate that during the past 11 ka 24 monogenetic basaltic eruptions occurred in the north sector of Gran Canaria. These eruptions can be grouped into three periods of eruptive activity: 1900–3200 ¹⁴C a BP; 5700–6000 ¹⁴C a BP; and an older period represented by only one eruption, El Draguillo, dated at 10 610 ± 190 ¹⁴C a BP. Archaeological studies have shown that the more recent eruptions affected prehistoric human settlements on the island. Field studies demonstrate that the eruptions typically built strombolian cones (30–250 m in height) and associated relatively long lava flows (100–10 350 m in length); a few eruptions also produced tephra fall deposits. The total erupted volume of these eruptions is about 0.388 km³ (46.1% as tephra fall, 41.8% as cinder cone deposits and 12.1% as lava flows). The relatively low eruption rate (～0.04 km³ ka^?1) during the past 11 ka is consistent with Gran Canaria's stage of evolution in the regional volcano‐tectonic setting of the Canary Archipelago. The results of our study were used to construct a volcanic hazards map that clearly delimits two sectors in the NE sector of Gran Canaria, where potential future eruptions would pose a substantial risk for densely populated areas. Copyright © 2009 John Wiley & Sons, Ltd.     

Morphologic evolution of the Central Andes of Peru

In this paper, we analyze the morphology of the Andes of Peru and its evolution based on the geometry of river channels, their bedrock profiles, stream gradient indices and the relation between thrust faults and morphology. The rivers of the Pacific Basin incised Mesozoic sediments of the Marañon thrust belt, Cenozoic volcanics and the granitic rocks of the Coastal Batholith. They are mainly bedrock channels with convex upward shapes and show signs of active ongoing incision. The changes in lithology do not correlate with breaks in slope of the channels (or knick points) such that the high gradient indices (K) with values between 2,000–3,000 and higher than 3,000 suggest that incision is controlled by tectonic activity. Our analysis reveals that many of the ranges of the Western Cordillera were uplifted to the actual elevations where peaks reach to 6,000 m above sea level by thrusting along steeply dipping faults. We correlate this uplift with the Quechua Phase of Neogene age documented for the Subandean thrust belt. The rivers of the Amazonas Basin have steep slopes and high gradient indices of 2,000–3,000 and locally more than 3,000 in those segments where the rivers flow over the crystalline basement of the Eastern Cordillera affected by vertical faulting. Gradient indices decrease to 1,000–2,000 within the east-vergent thrust belt of the Subandean Zone. Here a correlation between breaks in river channel slopes and location of thrust faults can be established, suggesting that the young, Quechua Phase thrust faults of the Subandean thrust belt, which involve Neogene sediments, influenced the channel geometry. In the eastern lowlands, these rivers become meandering and flow parallel to anticlines that formed in the hanging wall of Quechua Phase thrust faults, suggesting that the river courses were actively displaced outward into the foreland.     

Surface and groundwater pollution by organochlorine compounds in a typical soybean system from the south Pampa,Argentina

Organochlorine pesticides (OCPs) use has been restricted or forbidden in Argentina since 1998 and technical endosulfan is the last currently used OCPs on the soybean-wheat production. As they persist in soil for several years after application, OCPs constitute a source of environmental pollution. This work aims to assess OCPs contamination of groundwater (Gw) and streamwater (Sw) in the Quequén Grande River watershed from south Argentinean Pampas in relation to the hydrogeological characteristics. OCPs were analyzed in Sw, Gw, surface bottom sediments, soils and borehole cutting sediments (Cs) by gas chromatograph-electron capture detector. Pesticide distribution in Cs was dependent on the characteristic of the non-saturated zone. Leached pesticides over 3 m in Cs showed the pattern: HCHs = endosulfan > chlordanes > DDTs, and from 3 to 6 m heptachlor was the main group as a consequence of the past use of this compound in the area, mainly on potato crops. Endosulfan reaches Gw during application season as well as during flooding events while a retard effect was observed for Sw. Levels of α- and β-isomers were in certain cases above national (7 ng L⁻¹) and international (3 ng L⁻¹) limits for aquatic biota protection. As the endosulfan sulfate metabolite was present in Gw and Sw and due to its high toxicity, it should be considered in the establishment of water quality criteria for human and environmental protection.     

In situ LA-ICP-MS U–Pb titanite dating of Na–Ca metasomatism in orogenic belts: the North Pyrenean example

In the Pyrenees, in association with the rotation of the Iberian plate around Europe during the Mid-Cretaceous, a Na–Ca metasomatism is recognized as a complementary record of the hydrothermal activity that led to Na-metasomatism (albitization) and talc–chlorite mineralization. It affected metasedimentary rocks as well as Hercynian granites. In situ laser ablation ICP-MS U–Pb analyses of titanite grains formed in albitites during metasomatism date the Na–Ca metasomatism between 110 and 92 Ma. The temperature of the Na–Ca metasomatism is estimated to be approximately 550 °C. Both the time constraints and temperature estimates suggest that the Na–Ca metasomatism is related to the low-P high-T North Pyrenean metamorphism.     

Thermo-mechanical behavior of energy piles in high plasticity clays

Energy piles make use of constant and moderate ground temperature for efficient thermal control of buildings. However, this use introduces new engineering challenges because the changes of temperature in the foundation pile and ground induce additional deformations and forces in the foundation element and coupled thermo-hydro-mechanical phenomena in the soil. Several published full-scale tests investigated this aspect of energy piles and showed thermally induced deformation and forces in the foundation element. In parallel, significant progress has been made in the understanding of thermal properties of soils and on the effect of cyclic thermal load on ground and foundation behavior. However, the effect of temperature on the creep rate of energy piles has received practically no attention in the past. This paper reports the experimental results of an in situ tension thermo-mechanical test on an energy pile performed in a very stiff high plasticity clay. During the in situ test, the pile was subjected to thermal loading by circulating hot water in fitted pipes, simulating a thermal load in a cooling-dominated climate, at different levels of mechanical loading. The axial strain and temperature in the pile, and the load–displacement of the pile were monitored during the tension test at different locations along the center of the pile and at the pile head, respectively. The data showed that as the temperature increases, the observed creep rate of the energy pile in this high plasticity clay also increases, which will lead to additional time-dependent displacement of the foundation over the life time of the structure. It was also found that the use of geothermal piles causes practically insignificant thermally induced deformation and loads in the pile itself.     

Chromium oxidation by manganese (hydr)oxides in a California aquifer

There are increasing concerns with elevated levels of Cr(VI) in the environment because it is a strong oxidant, corrosive, and carcinogenic. The concerns extend to the presence of Cr(VI) in many aquifers in California and elsewhere, where relatively high levels have been attributed to both industrial pollution and natural processes. The authors have, therefore, determined if natural redox processes contribute to the presence of high Cr(VI) concentrations (6–36 μg L⁻¹) in an aquifer in central California relative to non-detectable concentrations (<0.1 μg L⁻¹) in an adjacent aquifer. Specifically, the distribution and the redox speciation of dissolved (<0.45 μm) Cr have been compared with those of particulate Mn and Fe oxy-hydroxides in sediments, using X-ray absorption spectroscopy at the Mn and Fe L-edges. The analyses show a correlation between the presence of dissolved Cr(VI) and Mn (hydr)oxide minerals, which are the only common, naturally occurring minerals known to oxidize Cr(III) in laboratory experiments. This covariance substantiates the results of those experiments and previous field studies that indicate natural oxidation mechanisms might account for the relatively high levels of Cr(VI) in the study site, as well as for elevated concentrations in other aquifers with similar biogeochemical conditions.