The importance of defining chemical potentials,substitution mechanisms and solubility in trace element diffusion studies: the case of Zr and Hf in olivine

The diffusion, substitution mechanism and solubility limits of Zr and Hf in synthetic forsterite (Mg₂SiO₄) and San Carlos olivine (Mg_0.9Fe_0.1)₂SiO₄ have been investigated between 1,200 and 1,500 °C as a function of the chemical potentials of the components in the system MgO(FeO)–SiO₂–ZrO₂(HfO₂). The effect of oxygen fugacity and crystallographic orientation were also investigated. The solubilities of Zr in forsterite are highest and diffusion fastest when the coexisting three-phase source assemblage includes ZrSiO₄ (zircon) or HfSiO₄ (hafnon), and lower and slower, respectively, when the source assemblage includes MgO (periclase). This indicates that Zr and Hf substitute on the octahedral sites in olivine, charge balanced by magnesium vacancies. Diffusion is anisotropic, with rates along the crystal axes increasing in the order a < b < c. The generalized diffusion relationship as a function of chemical activity (as \(a_{{{\text{SiO}}_{2} }}\)), orientation and temperature is: \(logD_{\text{Zr}} = \frac{1}{4}loga_{{{\text{SiO}}_{2} }} + logD_{0} - \left( {\frac{{368 \pm 17\;{\text{kJ}}\;{\text{mol}}^{ - 1} }}{{2.303\;{\text{RT}}}}} \right)\) where the values of log D ₀ are ?3.8(±0.5), ?3.4(±0.5) and ?3.1(±0.5) along the a, b and c axes, respectively. Most experiments were conducted in air (fO₂ = 10^?0.68 bars), but one at fO₂ = 10^?11.2 bars at 1,400 °C shows no resolvable effect of oxygen fugacity on Zr diffusion. Hf is slightly more soluble in olivine than Zr, but diffuses slightly slower. Diffusivities of Zr in experiments in San Carlos olivine at 1,400 °C, fO₂ = 10^?6.6 bars are similar to those in forsterite at the same conditions, showing that the controls on diffusivities are adequately captured by the simple system (nominally iron-free) experiments. Diffusivities are in good agreement with those measured by Spandler and O’Neill (Contrib Miner Petrol 159:791–818, 2010) in San Carlos olivine using silicate melt as the source at 1,300 °C, and fall within the range of most measurements of Fe–Mg inter-diffusion in olivine at this temperature. Forsterite–melt partitioning experiments in the CaO–MgO–Al₂O₃–SiO₂–ZrO₂/HfO₂ show that the interface concentrations from the diffusion experiments represent true equilibrium solubilities. Another test of internal consistency is that the ratios of the interface concentrations between experiments buffered by Mg₂SiO₄ + Mg₂Si₂O₆ + ZrSiO₄ or Mg₂SiO₄ + ZrSiO₄ + ZrO₂ (high silica activity) to those buffered by Mg₂SiO₄ + MgO + ZrO₂ (low silica activity) agree well with the ratios calculated from thermodynamic data. This study highlights the importance of buffering chemical potentials in diffusion experiments to provide constraints on the interface diffusant concentrations and hence validate the assumption of interface equilibrium.     

High-resolution aquifer analog of fluvial–aeolian sediments of the Guarani aquifer system

The Guarani aquifer system (GAS) represents one of the biggest aquifers in the world and is the most relevant groundwater resource in South America. For the first time, by combining field and laboratory measurements, a high-resolution aquifer analog model of fluvial–aeolian sediments of the GAS in São Paulo State (Brazil) is constructed. Three parallel sections of frontal outcrops, 28 m × 5.8 m, and two parallel sections of lateral outcrops, 7 m × 5.8 m, are recorded during open-pit mining of sandy sediments and describe in detail the three-dimensional distribution of the local lithofacies and hydrofacies. Variations of hydraulic conductivity, K, and porosity, n, are resolved on the centimeter scale, and the most permeable units of the fluvial–aeolian facies association are identified. The constructed aquifer analog model shows moderate hydraulic heterogeneity and a mean K value of 1.36 × 10^?4 m/s, which is greater than the reported range of K values for the entire GAS in São Paulo State. The results suggest that the examined sedimentary unit constitutes a relevant portion of the GAS in São Paulo State in the context of groundwater extraction and pollution. Moreover, the constructed aquifer analog is considered an ideal basis for future numerical model experiments, aiming at in-depth understanding of the groundwater flow and contaminant transport patterns at this GAS portion or at comparable fluvial–aeolian facies associations.     

Near-Sun Flux-Rope Structure of CMEs

We have used the Krall flux-rope model (Krall and St. Cyr, Astrophys. J. 2006, 657, 1740) (KFR) to fit 23 magnetic cloud (MC)-CMEs and 30 non-cloud ejecta (EJ)-CMEs in the Living With a Star (LWS) Coordinated Data Analysis Workshop (CDAW) 2011 list. The KFR-fit results shows that the CMEs associated with MCs (EJs) have been deflected closer to (away from) the solar disk center (DC), likely by both the intrinsic magnetic structures inside an active region (AR) and ambient magnetic structures (e.g. nearby ARs, coronal holes, and streamers, etc.). The mean absolute propagation latitudes and longitudes of the EJ-CMEs (18^°, 11^°) were larger than those of the MC-CMEs (11^°, 6^°) by 7^° and 5^°, respectively. Furthermore, the KFR-fit widths showed that the MC-CMEs are wider than the EJ-CMEs. The mean fitting face-on width and edge-on width of the MC-CMEs (EJ-CMEs) were 87 (85)^° and 70 (63)^°, respectively. The deflection away from DC and narrower angular widths of the EJ-CMEs have caused the observing spacecraft to pass over only their flanks and miss the central flux-rope structures. The results of this work support the idea that all CMEs have a flux-rope structure.     

The pseudometeorite Angara

Several pallasites are known to have formed strewn fields with multiple fragments. Therefore, it seems possible that the famous Krasnojarsk pallasite—the Pallas Iron of 687 kg—could have been accompanied by one or more additional fragments that had not been recovered due to incomplete observations from the overgrown and remote place of fall. During a survey for literature accounts of distant fragments in such a hypothetical strewn field, a report of native iron was found, dating to 1847. The fragments of nickel‐free iron—amounting to at least a few kg—had been recovered 1836–1843 during placer gold mining north of the Angara River. The position of these finds is coincident with Burovaya, Murozhna, and Uderei, the three known fragments of the pseudometeorite Angara, all collected in 1885.     

The Corossol structure: A possible impact crater on the seafloor of the northwestern Gulf of St. Lawrence,Eastern Canada

We report on a 4.1 (±0.2) km diameter and 185 m deep circular submarine structure exposed on the seabed in >40 m water depths in the northwestern Gulf of St. Lawrence (Eastern Canada) from the analysis of high‐resolution multibeam bathymetric and seismic data. The presence of a circular form characterized by a central uplift and concentric rings resembles the morphology and geometry of complex meteorite impact structures. Also, other origins, such as kimberlites, intrusions, karsts, or diapirs, can be eliminated on geological criteria. A single 4 cm long breccia fragment recovered from the central uplift has numerous glassy droplets of fluorapatite composition, assumed to be impact melts, and a single quartz grain with planar intersection features thought to be shock‐induced planar deformation features (PDFs). The absolute age of this possible impact structure is unknown, but its geological setting indicates that it was formed long after the Mid‐Ordovician and before regional pre‐Quaternary sea‐level lowstands. Present results outline the need for further examination to confirm an impact origin and to precisely date the formation of the structure.     

Diffusion and partition coefficients of minor and trace elements in San Carlos olivine at 1,300°C with some geochemical implications

Lattice diffusion coefficients have been determined for 19 elements (Li, Be, Na, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Y, Zr, Eu, Gd, Lu and Hf) in a single crystal of San Carlos olivine as a function of crystallographic orientation, at 1,300°C, 1 bar and fO₂ = 10^−8.3 bars, by equilibration with a synthetic silicate melt. Results for Li, Na, V, Cr, Fe and Zn are from diffusion of these elements out of the olivine, starting from their indigenous concentrations; those for all other elements are from diffusion into the olivine, from the silicate melt reservoir. Our 25-day experiment produced diffusion profiles 50 to > 700 μm in length, which are sufficiently long that precise analyses could be achieved by scanning laser ablation inductively coupled plasma mass spectrometry, even at concentration levels well below 1 μg g⁻¹. For the divalent cations Ca, Mn, Fe and Ni, profiles were also obtained by electron microprobe analysis. The results of the two methods agree well with each other, and are consistent with divalent cation diffusion coefficients previously determined using different experimental methodologies. Olivine/melt partition coefficients retrieved from the data are also consistent with other published partitioning data, indicating that element incorporation and transport in olivine in our experiment occurred via mechanisms appropriate to natural conditions. Most of the examined trace elements diffuse through olivine at similar rates to the major octahedral cations Fe and Mg, showing that cation charge and radius have little direct influence on diffusion rates. Aluminium and P remain low and constant in the olivine, implying negligible transport at our analytical scale, hence Al and P diffusion rates that are at least two orders of magnitude slower than the other cations studied here. All determined element diffusivities are anisotropic, with diffusion fastest along the [001] axis, except Y and the REEs, which diffuse isotropically. The results suggest that element diffusivity in olivine is largely controlled by cation site preference, charge balance mechanisms and point-defect concentrations. Elements that are present on multiple cation sites in olivine (e.g. Be and Ti) and trivalent elements that are charge-balanced by octahedral site vacancies tend to diffuse at relatively fast rates.     

<Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr anomalies in Late Cretaceous-Early Tertiary strata of the Cauvery basin,south India: Constraints on nature and rate of environmental changes across K-T boundary

The Ariyalur-Pondicherry sub-basin of the Cauvery basin comprises a near complete stratigraphic record of Upper Cretaceous-Lower Tertiary periods. Earlier studies have documented variations of clay mineral assemblages, change in microtexture of siliciclasts and many geochemical and stable isotopic anomalies far below the Cretaceous-Tertiary boundary (KTB) in these strata. This paper documents the occurrences of two positive ⁸⁷Sr/⁸⁶Sr anomalies preceding K-T boundary in this basin and discusses plausible causes. Analysis of trace elemental and stable isotopic profiles, sedimentation history, petrography and mineralogy of the rocks reveal that while both the anomalies may be due to increased detrital influx caused by sea level and climatic changes, the second anomaly might have been influenced by Deccan volcanism which in turn predated KTB. Record of such anomalies preceding K-T boundary supports the view of multi-causal step-wise extinction of biota across KTB.     

Determination of Selenium Concentrations in NIST SRM 610, 612, 614 and Geological Glass Reference Materials Using the Electron Probe, LA-ICP-MS and SHRIMP II

A combination of EMPA, sensitive high resolution ion microprobe (SHRIMP II) and/or LA-ICP-MS techniques was used to measure the concentration of selenium (Se) in NIST SRM 610, 612, 614 and a range of reference materials. Our new compiled value for the concentration of Se in NIST SRM 610 is 112 ± 2 μg g⁻¹. The concentration of Se in NIST SRM 612, using NIST SRM 610 for calibration, determined using LA-ICP-MS (confirmed using SHRIMP II) was 15.2 ± 0.2 μg g⁻¹. The concentration of Se in NIST SRM 614, using LA-ICP-MS was 0.394 ± 0.012 μg g⁻¹. LA-ICP-MS determination of Se in synthetic geological glasses BCR-2G, BIR-1G, TB-1G and the MPI-DING glasses showed a range in concentrations from 0.062 to 0.168 μg g⁻¹. Selenium in the natural glass, VG2, was 0.204 ± 0.028 μg g⁻¹.     

The Mechanism of Groundwater Salinization and Its Control in the Yaoba Oasis, Inner Mongolia

The arid area is one of the most concerned areas among the water resources researchers and economists. Northwest China will be an important developing region of China in the 21st century. Yaoba is a well-irrigation oasis within this arid area, which is located in the Alxa area west of the Helan Mountains and next to the Tengger desert in the east. It has contributed greatly to the local stock raising and agriculture since its development in 1970. However, the groundwater which the oasis depends on to survive has been getting salinized gradually and more serious in recent years.A comprehensive study was carried out using the methods of groundwater environment isotope analysis, lithofaci-es and palaeogeography, calculations of water-rock interaction and the existing form of chemical components in groundwater etc. It has been found that the salinization of groundwater is mainly caused by reinfiltration water solving the salt in soil which is deposited simultaneously with the sediments and accumulated in th     

Improved regional scale processes reflected in projected hydrological changes over large European catchments

For the fourth assessment report of the Intergovernmental Panel on Climate Change (IPCC), the recent version of the coupled atmosphere/ocean general circulation model (GCM) of the Max Planck Institute for Meteorology has been used to conduct an ensemble of transient climate simulations These simulations comprise three control simulations for the past century covering the period 1860–2000, and nine simulations for the future climate (2001–2100) using greenhouse gas (GHG) and aerosol concentrations according to the three IPCC scenarios B1, A1B and A2. For each scenario three simulations were performed. The global simulations were dynamically downscaled over Europe using the regional climate model (RCM) REMO at 0.44° horizontal resolution (about 50 km), whereas the physics packages of the GCM and RCM largely agree. The regional simulations comprise the three control simulations (1950–2000), the three A1B simulations and one simulation for B1 as well as for A2 (2001–2100). In our study we concentrate on the climate change signals in the hydrological cycle and the 2 m temperature by comparing the mean projected climate at the end of the twenty-first century (2071–2100) to a control period representing current climate (1961–1990). The robustness of the climate change signal projected by the GCM and RCM is analysed focussing on the large European catchments of Baltic Sea (land only), Danube and Rhine. In this respect, a robust climate change signal designates a projected change that sticks out of the noise of natural climate variability. Catchments and seasons are identified where the climate change signal in the components of the hydrological cycle is robust, and where this signal has a larger uncertainty. Notable differences in the robustness of the climate change signals between the GCM and RCM simulations are related to a stronger warming projected by the GCM in the winter over the Baltic Sea catchment and in the summer over the Danube and Rhine catchments. Our results indicate that the main explanation for these differences is that the finer resolution of the RCM leads to a better representation of local scale processes at the surface that feed back to the atmosphere, i.e. an improved representation of the land sea contrast and related moisture transport processes over the Baltic Sea catchment, and an improved representation of soil moisture feedbacks to the atmosphere over the Danube and Rhine catchments.