Cu- and Mn-bearing tourmalines from Brazil and Mozambique: crystal structures, chemistry and correlations

Cu- and Mn-bearing tourmalines from Brazil and Mozambique were characterised chemically (EMPA and LA-ICP-MS) and by X-ray single-crystal structure refinement. All these samples are rich in Al, Li and F (fluor-elbaite) and contain significant amounts of CuO (up to ~1.8 wt%) and MnO (up to ~3.5 wt%). Structurally investigated samples show a pronounced positive correlation between the <Y-O> distances and the (Li + Mn²⁺ + Cu + Fe²⁺) content (apfu) at this site with R ² = 0.90. An excellent negative correlation exists between the <Y-O> distances and the Al₂O₃ content (R ² = 0.94). The samples at each locality generally show a strong negative correlation between the X-site vacancies and the (MnO + FeO) content. The Mn content in these tourmalines depends on the availability of Mn, on the formation temperature, as well as on stereochemical constraints. Because of a very weak correlation between MnO and CuO we believe that the Cu content in tourmaline is essentially dependent on the availability of Cu and on stereochemical constraints.     

Multi-metal contaminant dynamics in temporarily flooded soil under sulfate limitation

In many river basins, floodplain soils have accumulated a variety of metal contaminants, which might be released during periods of flooding. We investigated the dynamics of copper, cadmium, lead, zinc, and nickel in a contaminated freshwater floodplain soil under a realistic sulfate-limited flooding regime in microcosm experiments. We found that most contaminants were initially mobilized by processes driven by the reductive dissolution of Fe(III) and Mn(IV, III) (hydr)oxides. Subsequently, bacterial sulfate respiration resulted in the transformation of the entire available sulfate (2.3 mmol/kg) into chromous reducible sulfur (CRS). Cu K-edge X-ray absorption fine structure (XAFS) spectroscopy revealed that the soil Cu speciation changed from predominantly Cu(II) bound to soil organic matter (SOM) intermittently to 14% metallic Cu(0) and subsequently to 66% copper sulfide (Cu_xS). These Cu_xS precipitates accounted for most of the formed CRS, suggesting that Cu_xS was the dominant sulfide phase formed in the flooded soil. Sequential metal extractions, in agreement with CRS results, suggested that easily mobilizable Cd was completely and Pb partially sequestered in sulfide precipitates, controlling their dissolved concentrations to below detection limits. In contrast, Zn and Ni (as well as Fe) were hardly sequestered into sulfide phases, so that micromolar levels of dissolved Zn and Ni (and millimolar dissolved Fe(II)) persisted in the reduced soil. The finding that Cu, Cd, and Pb were sequestered (but hardly any Zn, Ni, and Fe) is consistent with the thermodynamically predicted sulfide ladder following the increasing solubility products of the respective metal sulfides. The observation that Cd and Pb were sequestered in sulfides despite the presence of remaining SOM-bound Cu(II) suggested that the kinetics of Cu(II) desorption, diffusion, and/or Cu_xS precipitation interfered with the sulfide ladder. We conclude that the dynamics of multiple metal contaminants are intimately coupled under sulfate limitation by the relative thermodynamic stabilities and formation kinetics of the respective metal sulfides.     

Rapid and cyclic aeolian deposition during the Last Glacial in European loess: a high-resolution record from Nussloch, Germany

This paper reports the results of an investigation of the Weichselian Upper Pleniglacial loess sequences of Nussloch (Rhine Valley, Germany) based on stratigraphy, palaeopedology, sedimentology, palynology, malacology and geochemistry (δ¹³C), supported by radiocarbon, TL and OSL dating. Grain-size and magnetic susceptibility records are taken at 5 cm intervals from the Upper Pleniglacial (UPG) loess. The data indicate cyclic variations in loess deposition between ca 34 and 17 ka, when the sedimentation rate is especially high (1.0–1.2 m per ka for more than 10 m). The grain-size index (GSI: ratio of coarse silt versus fine silt and clay) shows variations, which are assumed to be an indirect measurement of wind intensity. The sedimentation rate, interpreted from the profiles, indicates high values in loess (Loess events LE-1 to LE-7) and low or negligible values in tundra gley horizons G1 to G8. OSL ages from the loess and ¹⁴C dates from organic matter in the loess show that loess deposition was rapid but was interrupted by shorter periods of reduced aeolian sedimentation. Comparison between the data from Nussloch and other European sequences demonstrates a progressive coarsening of the loess deposits between ca 30 and 22 ka. This coarsening trend ends with a short but major grain-size decrease and is followed by an increase to a new maximum at 20 ± 2 ka (“W” shape). Correlation between the loess GSI and the Greenland ice-core dust records, suggests a global connection between North Atlantic and Western European global atmospheric circulation and wind regimes. In addition, the typical Upper Pleniglacial loess deposition begins at ca 30–31 ka, close to Heinrich event (HE) 3, and the main period of loess sedimentation at about 25 ± 2 ka is coeval to HE 2. Correlation of magnetic susceptibility and grain-size records shows that the periods, characterised by high GSI, coincide with an increase in the amount of ferromagnetic minerals reworked from the Rhine alluvial plain. They suggest enhancement in the frequency of the storms from N–NW. These results are integrated within a palaeogeographical model of dust transport and deposition in Western Europe for the Weichselian Upper Pleniglacial (or Late Pleniglacial).     

Did the 7/9/1999 M5.9 Athens Earthquake Come with a Warning?

Prior to the 7/9/1999 M_S = 5.9 Athens earthquake, regional seismicity has exhibited a power-law increase, of the form = K+A(t_c - t)ⁿ, where is estimated using an expression log = cM + d and t_c is the time of the culminating event. Such changes appeared after the 17/8/1999 M7.4 Izmit event. We quantified the performance of the power law vs. the null hypothesis of constant seismic release rates, by defining the curvature C as the ratio of the power law fit RMS/linear fit RMS, so that the smaller C is, the better the power law behaviour. By mapping C, we have established a critical radius of 110 km and observed that the region of correlated accelerating seismic release extended from the N. Aegean, through Euboea and Attica to the SW Peloponnese. A few days prior to the Athens event, min(C) was centred at the epicentral area and numerical simulation yielded t_c = 1999.676 and predicted M_S = 5.77. Seismicity rates returned to normal (quasi-constant) after the Athens event. We interpret this effect as critical point behaviour, following remote excitation of a broad area by stress redistribution due to the Izmit event which, at Athens, has triggered `premature' failure of a fault nearing its load bearing capacity. If this is correct, we have documented a case of remote earthquake triggering by another earthquake, as well as insight into the mechanisms producing it. As a corollary, we note that a large event may beget another large event in its broader region of interaction, which may be preceded by characteristic precursory seismicity changes.     

Melt extraction pathways and stagnation depths beneath the Madeira and Desertas rift zones (NE Atlantic) inferred from barometric studies

The Madeira and Desertas Islands (eastern North Atlantic) show well-developed rift zones which intersect near the eastern tip of Madeira (São Lourenço peninsula). We applied fluid inclusion barometry and clinopyroxene-melt thermobarometry to reconstruct levels of magma stagnation beneath the two adjacent rifts and to examine a possible genetic relationship during their evolution. Densities of CO₂-dominated fluid inclusions in basanitic to basaltic samples from São Lourenço yielded frequency maxima at pressures of 0.57–0.87 GPa (23–29 km depth) and 0.25–0.32 GPa (8–10 km), whereas basanites, basalts and xenoliths from the Desertas indicate 0.3–0.72 GPa (10–24 km) and 0.07–0.12 GPa (2–3 km). Clinopyroxene-melt thermobarometry applied to Ti-augite phenocryst rim and glass/groundmass compositions indicates pressures of 0.45–1.06 GPa (15–35 km; São Lourenço) and 0.53–0.89 GPa (17–28 km; Desertas Islands) which partly overlap with pressures indicated by fluid inclusions. We interpret our data to suggest a multi-stage magma ascent beneath the Madeira Archipelago: main fractionation occurs at multiple levels within the mantle (>15 km depth) and is followed by temporary stagnation within the crust prior to eruption. Depths of crustal magma stagnation beneath São Lourenço and the Desertas differ significantly, and there is no evidence for a common shallow magma reservoir feeding both rift arms. We discuss two models to explain the relations between the two adjacent rift systems: Madeira and the Desertas may represent either a two-armed rift system or two volcanic centres with separate magma supply systems. For petrological and volcanological reasons, we favour the second model and suggest that Madeira and the Desertas root in distinct regions of melt extraction. Magma focusing into the Desertas system off the hotspot axis may result from lithospheric bending caused by the load of the Madeira and Porto Santo shields, combined with regional variations in melt production due to an irregularly shaped plume.Electronic Supplementary Material Supplementary material is available for this article if you access the article at . A link in the frame on the left on that page takes you directly to the supplementary material.Editorial responsibility: J. Hoefs     

Morphological evolution of dissolving feldspar particles with anisotropic surface kinetics and implications for dissolution rate normalization and grain size dependence: A kinetic modeling study

With previous two-dimensional (2D) simulations based on surface-specific feldspar dissolution succeeding in relating the macroscopic feldspar kinetics to the molecular-scale surface reactions of Si and Al atoms ( [Zhang and Lüttge, 2008] and [Zhang and Lüttge, 2009]), we extended our modeling effort to three-dimensional (3D) feldspar particle dissolution simulations. Bearing on the same theoretical basis, the 3D feldspar particle dissolution simulations have verified the anisotropic surface kinetics observed in the 2D surface-specific simulations. The combined effect of saturation state, pH, and temperature on the surface kinetics anisotropy has been subsequently evaluated, found offering diverse options for morphological evolution of dissolving feldspar nanoparticles with varying grain sizes and starting shapes. Among the three primary faces on the simulated feldspar surface, the (1 0 0) face has the biggest dissolution rate across an extensively wide saturation state range and thus acquires a higher percentage of the surface area upon dissolution. The slowest dissolution occurs to either (0 0 1) or (0 1 0) faces depending on the bond energies of Si-(O)-Si (Φ_Si-O-Si/kT) and Al-(O)-Si (Φ_Al-O-Si/kT). When the ratio of Φ_Si-O-Si/kT to Φ_Al-O-Si/kT changes from 6:3 to 7:5, the dissolution rates of three primary faces change from the trend of (1 0 0) > (0 1 0) > (0 0 1) to the trend of (1 0 0) > (0 0 1) > (0 1 0). The rate difference between faces becomes more distinct and accordingly edge rounding becomes more significant. Feldspar nanoparticles also experience an increasing degree of edge rounding from far-from-equilibrium to close-to-equilibrium. Furthermore, we assessed the connection between the continuous morphological modification and the variation in the bulk dissolution rate during the dissolution of a single feldspar particle. Different normalization treatments equivalent to the commonly used mass, cube assumption, sphere assumption, geometric surface area, and reactive surface area normalizations have been used to normalize the bulk dissolution rate. For each of the treatments, time consistence and grain size dependence of the normalized dissolution rate have been evaluated and the results revealed significant dependences on the magnitude of surface kinetic anisotropy under differing environmental conditions. In general, the normalized dissolution rates are strongly dependent on grain size. Time-consistent normalization treatment varies with the investigated condition. The modeling results suggest that the sphere-, cube-, and BET-normalized dissolution rates are appropriate under the far-from-equilibrium conditions at low pH where these normalizations are time-consistent and are slightly dependent on grain size.     

Fe and O isotope composition of meteorite fusion crusts: Possible natural analogues to chondrule formation?

Meteorite fusion crust formation is a brief event in a high‐temperature (2000–12,000 K) and high‐pressure (2–5 MPa) regime. We studied fusion crusts and bulk samples of 10 ordinary chondrite falls and 10 ordinary chondrite finds. The fusion crusts show a typical layering and most contain vesicles. All fusion crusts are enriched in heavy Fe isotopes, with δ⁵⁶Fe values up to +0.35‰ relative to the solar system mean. On average, the δ⁵⁶Fe of fusion crusts from finds is +0.23‰, which is 0.08‰ higher than the average from falls (+0.15‰). Higher δ⁵⁶Fe in fusion crusts of finds correlate with bulk chondrite enrichments in mobile elements such as Ba and Sr. The δ⁵⁶Fe signature of meteorite fusion crusts was produced by two processes (1) evaporation during atmospheric entry and (2) terrestrial weathering. Fusion crusts have either the same or higher δ¹⁸O (0.9–1.5‰) than their host chondrites, and the same is true for Δ¹⁷O. The differences in bulk chondrite and fusion crust oxygen isotope composition are explained by exchange of oxygen between the molten surface of the meteorites with the atmosphere and weathering. Meteorite fusion crust formation is qualitatively similar to conditions of chondrule formation. Therefore, fusion crusts may, at least to some extent, serve as a natural analogue to chondrule formation processes. Meteorite fusion crust and chondrules exhibit a similar extent of Fe isotope fractionation, supporting the idea that the Fe isotope signature of chondrules was established in a high‐pressure environment that prevented large isotope fractionations. The exchange of O between a chondrule melt and an ¹⁶O‐poor nebula as the cause for the observed nonmass dependent O isotope compositions in chondrules is supported by the same process, although to a much lower extent, in meteorite fusion crusts.     

The solution topology of galactic winds

The system of ordinary differential equations derived from the hydrodynamical equations of a radially symmetric flow has a one dimensional manifold of critical points if there is mass loading in the flow or if the heating and cooling rates are taken to be independent of the thermodynamic variables as is usual.     

The constancy of galactic cosmic rays as recorded by cosmogenic nuclides in iron meteorites

We measured the He, Ne, and Ar isotopic concentrations and the ¹⁰Be, ²⁶Al, ³⁶Cl, and ⁴¹Ca concentrations in 56 iron meteorites of groups IIIAB, IIAB, IVA, IC, IIA, IIB, and one ungrouped. From ⁴¹Ca and ³⁶Cl data, we calculated terrestrial ages indistinguishable from zero for six samples, indicating recent falls, up to 562 ± 86 ka. Three of the studied meteorites are falls. The data for the other 47 irons confirm that terrestrial ages for iron meteorites can be as long as a few hundred thousand years even in relatively humid conditions. The ³⁶Cl‐³⁶Ar cosmic ray exposure (CRE) ages range from 4.3 ± 0.4 Ma to 652 ± 99 Ma. By including literature data, we established a consistent and reliable CRE age database for 67 iron meteorites. The high quality of the CRE ages enables us to study structures in the CRE age histogram more reliably. At first sight, the CRE age histogram shows peaks at about 400 and 630 Ma. After correction for pairing, the updated CRE age histogram comprises 41 individual samples and shows no indications of temporal periodicity, especially not if one considers each iron meteorite group separately. Our study contradicts the hypothesis of periodic GCR intensity variations (Shaviv 2002, 2003), confirming other studies indicating that there are no periodic structures in the CRE age histogram (e.g., Rahmstorf et al. 2004; Jahnke 2005). The data contradict the hypothesis that periodic GCR intensity variations might have triggered periodic Earth climate changes. The ³⁶Cl‐³⁶Ar CRE ages are on average 40% lower than the ⁴¹K‐K CRE ages (e.g., Voshage 1967). This offset can either be due to an offset in the ⁴¹K‐K dating system or due to a significantly lower GCR intensity in the time interval 195–656 Ma compared to the recent past. A 40% lower GCR intensity, however, would have increased the Earth temperature by up to 2 °C, which seems unrealistic and leaves an ill‐defined ⁴¹K‐K CRE age system the most likely explanation. Finally, we present new ²⁶Al/²¹Ne and ¹⁰Be/²¹Ne production rate ratios of 0.32 ± 0.01 and 0.44 ± 0.03, respectively.     

Carry-over effects of the membrane interface probe

The membrane interface probe (MIP) is widely used to characterize the subsurface distribution of volatile organic compounds (VOCs). One problem that arises during MIP application is that disproportionately high MIP signals are obtained after passing source zones which contain mobile or residual phases. This serious problem occurs because of a carry-over effect, in particular caused by compound-specific retention times in the conventional unheated transfer line, commonly used during such an investigation. The objective of this study was to perform a qualitative methodical field evaluation of the carry-over effect of a conventional MIP system with a conventional unheated transfer line. This was achieved by coupling a mobile mass spectrometer to the MIP device. Results obtained were then further compared with those achieved using a laser induced fluorescence (LIF) system. Because of this coupling, time- and depth-dependent signals for different substances became known. Field evaluation data obtained showed complex superpositions of compounds with MIP system results. As a result of this superposition, MIP signals from the saturated zone beneath the source zone (zone with free and/or residual phase) are blurred and are therefore not representative of particular depths. However, utilizing multidirectional probing alongside conventional MIP probing (forwards and backwards), it was possible to detect the upper and lower phase boundary of the source zone. These MIP results correlated excellently with the LIF results. An important conclusion that can be drawn from the field investigation is that coupling a mobile mass spectrometer to the MIP system enables advanced MIP signal interpretation to be successfully achieved.