Geochemistry of highly acidic mine water following disposal into a natural lake with carbonate bedrock

Acid mine drainage (AMD) from the Zn–Pb(–Ag–Bi–Cu) deposit of Cerro de Pasco (Central Peru) and waste water from a Cu-extraction plant has been discharged since 1981 into Lake Yanamate, a natural lake with carbonate bedrock. The lake has developed a highly acidic pH of ∼1. Mean lake water chemistry was characterized by 16,775 mg/L acidity as CaCO₃, 4330 mg/L Fe and 29,250 mg/L SO₄. Mean trace element concentrations were 86.8 mg/L Cu, 493 mg/L Zn, 2.9 mg/L Pb and 48 mg/L As, which did not differ greatly from the discharged AMD. Most elements showed increasing concentrations from the surface to the lake bottom at a maximal depth of 41 m (e.g. from 3581 to 5433 mg/L Fe and 25,609 to 35,959 mg/L SO₄). The variations in the H and O isotope compositions and the element concentrations within the upper 10 m of the water column suggest mixing with recently discharged AMD, shallow groundwater and precipitation waters. Below 15 m a stagnant zone had developed. Gypsum (saturation index, SI ∼ 0.25) and anglesite (SI ∼ 0.1) were in equilibrium with lake water. Jarosite was oversaturated (SI ∼ 1.7) in the upper part of the water column, resulting in downward settling and re-dissolution in the lower part of the water column (SI ∼ −0.7). Accordingly, jarosite was only found in sediments from less than 7 m water depth. At the lake bottom, a layer of gel-like material (∼90 wt.% water) of pH ∼1 with a total organic C content of up to 4.40 wet wt.% originated from the kerosene discharge of the Cu-extraction plant and had contaminant element concentrations similar to the lake water. Below the organic layer followed a layer of gypsum with pH 1.5, which overlaid the dissolving carbonate sediments of pH 5.3–7. In these two layers the contaminant elements were enriched compared to lake water in the sequence As < Pb ≈ Cu < Cd < Zn = Mn with increasing depth. This sequence of enrichment was explained by the following processes: (i) adsorption of As on Fe-hydroxides coating plant roots at low pH (up to 3326 mg/kg As), (ii) adsorption at increasing pH near the gypsum/calcite boundary (up to 1812 mg/kg Pb, 2531 mg/kg Cu, and 36 mg/kg Cd), and (iii) precipitation of carbonates (up to 5177 mg/kg Zn and 810 mg/kg Mn; all data corrected to a wet base). The infiltration rate was approximately equal to the discharge rate, thus gypsum and hydroxide precipitation had not resulted in complete clogging of the lake bedrocks.     

Ancient graphite in the Eoarchean quartz-pyroxene rocks from Akilia in southern West Greenland II: Isotopic and chemical compositions and comparison with Paleoproterozoic banded iron formations

We present detailed petrographic surveys of apatite grains in association with carbonaceous material (CM) in two banded iron formations (BIFs) from the Paleoproterozoic of Uruguay and Michigan for comparison with similar mineral associations in the highly debated Akilia Quartz-pyroxene (Qp) rock. Petrographic and Raman spectroscopic surveys of these Paleoproterozoic BIFs show that apatite grains typically occur in bands parallel to bedding and are more often associated with CM when concentrations of organic matter are high. Carbonaceous material in the Vichadero BIF from Uruguay is generally well-crystallized graphite and occurs in concentrations around 0.01 wt% with an average δ¹³C_gra value of −28.6 ± 4.4‰ (1σ). In this BIF, only about 5% of apatite grains are associated with graphite. In comparison, CM in the Bijiki BIF from Michigan is also graphitic, but occurs in concentrations around 2.4 wt% with δ¹³C_gra values around −24.0 ± 0.3‰ (1σ). In the Bijiki BIF, more than 78% of apatite grains are associated with CM. Given the geologic context and high levels of CM in the Bijiki BIF, the significantly higher proportion of apatite grains associated with CM in this rock is interpreted to represent diagenetically altered biomass and shows that such diagenetic mineral associations can survive metamorphism up to the amphibolite facies.Isotope compositions of CM in muffled acidified whole-rock powders from the Akilia Qp rock have average δ¹³C_gra values of −17.5 ± 2.5‰ (1σ), while δ¹³C_carb values in whole-rock powders average −4.0 ± 1.0‰ (1σ). Carbon isotope compositions of graphite associated with apatite and other minerals in the Akilia Qp rock were also measured with the NanoSIMS to have similar ranges of δ¹³C_gra values averaging −13.8 ± 5.6‰ (1σ). The NanoSIMS was also used to semi-quantitatively map the distributions of H, N, O, P, and S in graphite from the Akilia Qp rock, and relative abundances were found to be similar for graphite associated with apatite or with hornblende, calcite, and sulfides. These analyses revealed generally lower abundances of trace elements in the Akilia graphite compared to graphite associated with apatite from Paleoproterozoic BIFs.Graphite associated with hornblende, calcite, and sulfides in the Akilia Qp rock was fluid-deposited at high-temperature from carbon-bearing fluids, and since this graphite has similar ranges of δ¹³C_gra values and of trace elements compared to graphite associated with apatite, we conclude that the Akilia graphite in different mineral associations formed from the same source(s) of CM. Collectively our results do not exclude a biogenic origin of the carbon in the Akilia graphite, but because some observations can not exclude graphitization of abiogenic carbon from CO₂- and CH₄-bearing mantle fluids, there remain ambiguities with respect to the exact origin of carbon in this ancient metasedimentary rock. Accordingly, there may have been several generations of graphite formation along with possibly varying mixtures of CO₂- and CH₄-bearing fluids that may have resulted in large ranges of δ¹³C_gra values. The possibility of fluid-deposited graphite associated with apatite should be a focus of future investigations as this may prove to be an alternative pathway of graphitization from phosphate-bearing fluids. Correlated micro-analytical approaches tested on terrestrial rocks in this work provide insights into the origin of carbon in ancient graphite and will pave the way for the search for life on other ancient planetary surfaces.     

A redetermination of the isotopic abundances of atmospheric Ar

Atmospheric argon measured on a dynamically operated mass spectrometer with an ion source magnet, indicated systematically larger ⁴⁰Ar/³⁶Ar ratios compared to the generally accepted value of Nier [Nier A.O., 1950. A redetermination of the relative abundances of the isotopes of carbon, nitrogen, oxygen, argon, and potassium. Phys. Rev. 77, 789-793], 295.5 ± 0.5, which has served as the standard for all isotopic measurements in geochemistry and cosmochemistry. Gravimetrically prepared mixtures of highly enriched ³⁶Ar and ⁴⁰Ar were utilized to redetermine the isotopic abundances of atmospheric Ar, using a dynamically operated isotope ratio mass spectrometer with minor modifications and special gas handling techniques to avoid fractionation. A new ratio ⁴⁰Ar/³⁶Ar = 298.56 ± 0.31 was obtained with a precision of 0.1%, approximately 1% higher than the previously accepted value. Combined with the ³⁸Ar/³⁶Ar (0.1885 ± 0.0003) measured with a VG5400 noble gas mass spectrometer in static operation, the percent abundances of ³⁶Ar, ³⁸Ar, and ⁴⁰Ar were determined to be 0.3336 ± 0.0004, 0.0629 ± 0.0001, and 99.6035 ± 0.0004, respectively. We calculate an atomic mass of Ar of 39.9478 ± 0.0002. Accurate Ar isotopic abundances are relevant in numerous applications, as the calibration of the mass spectrometer discrimination.     

Radio Observations of the 20 January 2005 X-class Flare

We present a multi-frequency and multi-instrument study of the 20 January 2005 event. We focus mainly on the complex radio signatures and their association with the active phenomena taking place: flares, CMEs, particle acceleration, and magnetic restructuring. As a variety of energetic-particle accelerators and sources of radio bursts are present, in the flare – ejecta combination, we investigate their relative importance in the progress of this event. The dynamic spectra of ARTEMIS-IV – Wind/Waves – HiRAS, with 2000 MHz – 20 kHz frequency coverage, were used to track the evolution of the event from the low corona to the interplanetary space; these were supplemented with SXR, HXR, and γ-ray recordings. The observations were compared with the expected radio signatures and energetic-particle populations envisaged by the Standard Flare – CME model and the reconnection outflow termination shock model. A proper combination of these mechanisms seems to provide an adequate model for the interpretation of the observational data.     

Geological observations in high‐grade mid‐Proterozoic rocks from Else Platform,northern Prince Charles mountains region,east Antarctica

Granulite facies rocks on Else Platform in the northern Prince Charles Mountains, east Antarctica, consist of metasedimentary gneiss extensively intruded by granitic rocks. The dominant rock type is a layered garnetbiotite‐bearing gneiss intercalated with minor garnet‐cordierite‐sillimanite gneiss and calc‐silicate. Voluminous megacrystic granite intruded early during a mid‐Proterozoic (ca 1000 Ma) granulite event, M₁, widely recognized in east Antarctica. Peak metamorphic conditions for M₁ are in the range of 650–750 MPa at ～800°C and were associated with the development of a gneissic foliation, S₁ and steep east‐plunging lineation, L₁. Strain partitioning during progressive non‐coaxial deformation formed large D₂ granulite facies south‐dipping thrusts, with a steep, east‐plunging lineation. In areas of lower D₂ strain, large‐scale upright, steep east‐plunging fold structures formed synchronously with the D₂ high‐strain zones. Voluminous garnet‐bearing leucogneiss intruded at 940 ±20 Ma and was deformed in the D₂ high‐strain zones. Textural relationships in pelitic rocks show that peak‐M2 assemblages formed during increasing temperatures via reactions such as biotite + sillimanite + quartz ± plagioclase = spinel + cordierite + ilmenite + K‐feldspar + melt. In biotite‐absent rocks, re‐equilibration of deformed M₁ garnet‐sillimanite‐ilmenite assemblages occurred through decompressive reactions of the form, garnet + sillimanite + ilmenite = cordierite + spinel + quartz. Pressure/temperature estimates indicate that peak‐M₂ conditions were 500–600 MPa and 700±50°C. At about 500 Ma, north‐trending granitic dykes intruded and were deformed during D₃‐M₃ at probable upper amphibolite facies conditions. Cooling from peak D₃‐M₃ conditions was associated with the formation of narrow greenschist facies shear zones, and the intrusion of pegmatite. Cross‐cutting all features are abundant north‐south trending alkaline mafic dykes that were emplaced over the interval ca 310–145 Ma, reflecting prolonged intrusive activity. Some of the dykes are associated with steeply dipping faults that may be related to basin formation during Permian times and later extension, synchronous with the formation of the Lambert Graben in the Cretaceous.     

Consequences of climate change for the soil climate in Central Europe and the central plains of the United States

This study aims to evaluate soil climate quantitatively under present and projected climatic conditions across Central Europe (12.1°–18.9° E and 46.8°–51.1° N) and the U.S. Central Plains (90°–104° W and 37°–49° N), with a special focus on soil temperature, hydric regime, drought risk and potential productivity (assessed as a period suitable for crop growth). The analysis was completed for the baselines (1961–1990 for Europe and 1985–2005 for the U.S.) and time horizons of 2025, 2050 and 2100 based on the outputs of three global circulation models using two levels of climate sensitivity. The results indicate that the soil climate (soil temperature and hydric soil regimes) will change dramatically in both regions, with significant consequences for soil genesis. However, the predicted changes of the pathways are very uncertain because of the range of future climate systems predicted by climate models. Nevertheless, our findings suggest that the risk of unfavourable dry years will increase, resulting in greater risk of soil erosion and lower productivity. The projected increase in the variability of dry and wet events combined with the uncertainty (particularly in the U.S.) poses a challenge for selecting the most appropriate adaptation strategies and for setting adequate policies. The results also suggest that the soil resources are likely be under increased pressure from changes in climate.     

Polyphase strain caps

Strain caps are one of a series of microstructures that typically form during deformation of a softer matrix around hard objects. However??in contrast to other microstructures around porphyroblasts, for example pressure shadows??strain caps are rarely described in the literature. Here we describe strain caps with particular focus on strain caps associated with growth of a new phase, not elsewhere present in the paragenesis. Examples from foliated, amphibolite facies, metapelitic schists from Alaska, Sinai and Bhutan are discussed. All examples show chlorite growth exclusively in strain caps formed around porphyroblasts. Porphyroblasts around which the strain caps grow are muscovite, staurolite and garnet, respectively. In all of these examples strain caps formed synkinematically, but the chlorite grew statically at a later stage. Three mechanisms can explain the formation of new phases in the strain cap region: (a) the strain cap region may have experienced different P-T conditions from the matrix; (b) the strain cap region has a different effective bulk composition from the surrounding matrix; (c) fluid flow that is preferentially focused parallel to the foliation planes causing only local adjustment to retrograde metamorphism in the strain cap region. We show that the third hypothesis is the most preferable mechanism. Indeed, the absence of chlorite outside the strain cap region allows a quantification of the amount of fluid that infiltrated the rock. It is shown that for Bhutan sample about 8.5 mole% more water must have been added to the rock during fluid infiltration to cause the strain cap formation.