Zircon response to high-grade metamorphism as revealed by U–Pb and cathodoluminescence studies

Correct interpretation of zircon ages from high-grade metamorphic terrains poses a major challenge because of the differential response of the U–Pb system to metamorphism, and many aspects like pressure–temperature conditions, metamorphic mineral transformations and textural properties of the zircon crystals have to be explored. A large (c. 450?km²) coherent migmatite complex was recently discovered in the Bohemian Massif, Central European Variscides. Rocks from this complex are characterized by granulite- and amphibolite-facies mineral assemblages and, based on compositional and isotopic trends, are identified as the remnants of a magma body derived from mixing between tonalite and supracrustal rocks. Zircon crystals from the migmatites are exclusively large (200–400?μm) and yield ²⁰⁷Pb/²⁰⁶Pb evaporation ages between 342–328?Ma and single-grain zircon fractions analysed by U–Pb ID-TIMS method plot along the concordia curve between 342 and 325?Ma. High-resolution U–Pb SHRIMP analyses substantiate the existence of a resolvable age variability and yield older ²⁰⁶Pb/²³⁸U ages (342–330?Ma, weighted mean age?=?333.6?±?3.1?Ma) for inner zone domains without relict cores and younger ²⁰⁶Pb/²³⁸U ages (333–320?Ma, weighted mean age?=?326.0?±?2.8?Ma) for rim domains. Pre-metamorphic cores were identified only in one sample (²⁰⁶Pb/²³⁸U ages at 375.0?±?3.9, 420.3?±?4.4 and 426.2?±?4.4?Ma). Most zircon ages bracket the time span between granulite-facies metamorphism in the Bohemian Massif (~345?Ma) and the late-Variscan anatectic overprint (Bavarian phase, ~325?Ma). It is argued that pre-existing zircon was variously affected by these metamorphic events and that primary magmatic growth zones were replaced by secondary textures as a result of diffusion reaction processes and replacement of zircon by dissolution and recrystallization followed by new zircon rim growth. Collectively, the results show that the zircons equilibrated during high-grade metamorphism and record partial loss of radiogenic Pb during post-peak granulite events and new growth under subsequent anatectic conditions.     

Magnetic anisotropy of hematite natural crystals: increasing low-field strength experiments

Hematite is a very abundant mineral in natural rock samples. Despite being one of the most important carriers of remanent magnetization, its magnetic anisotropy is not well understood partially due to its high coercivity and complex behavior. In particular, the field intensity beyond which the Rayleigh relation no longer holds varies from one crystal to another. This field threshold is usually less than the field used in most commercial instruments. The nonlinear behavior of low-field susceptibility may thus hinder the magnetic fabric analysis. We have carried out an intensive study of the low-field bulk susceptibility and anisotropy of magnetic susceptibility (AMS) at increasing low fields in the range of 2–450 A/m (effective value) in a collection of hematite natural crystals. Standard rock magnetic properties, X-ray diffraction, and mass spectrometry have also been determined in order to discover the parameters influencing the low-field susceptibility variations with field. The AMS principal directions, the shape of the AMS ellipsoid, and the degree of anisotropy are the parameters that can vary with different applied fields. It has been found that there is no correlation between magnetic properties like coercivity or saturation magnetization and the range in which the Rayleigh approximation is valid. However, there seems to be a correlation with the peak width determined from X-ray diffraction, suggesting that the Rayleigh region in hematite crystals is related to the spatial orientation of the physical domains within the basal plane.     

A new approach to modeling perpendicular fabrics in porphyritic plutonic rocks using the finite element method

A growing body of field evidence indicates that hypersolidus fabrics preserved in syntectonic plutons are likely to have formed in highly crystallized ‘rigid sponge’ magma. This paper demonstrates that such magma could be idealized as a rheological solid and that the development of non-coaxial fabrics in plutonic rocks can very conveniently be modeled in the framework of solid mechanics. Using the finite element method (FEM), we modeled two strain regimes of small magnitudes (plane-strain horizontal simple shear with the shear strain γ of up to 0.30 and plane-strain pure shear of up to 15% shortening) superposed onto vertically oriented and variously spaced elastic phenocrysts set in the viscoelastic matrix. In the simple shear regime, the phenocrysts slightly rotate toward the shear plane, while the principal strain directions in the matrix are instantaneously oriented at an angle of about 45° or less to the phenocryst fabric. Simple shear thus can only lead to the formation of oblique phenocryst and matrix fabrics. By contrast, the vertical phenocryst fabric is maintained in the pure shear regime, and a new horizontal fabric can develop almost instantaneously in the matrix even for small amounts of superposed shortening (5% shortening after 10 ky in our model). We conclude that such a mechanism can easily produce perpendicular hypersolidus fabrics in plutonic rocks and that only a very short time span (first thousands of years) is required to develop magmatic fabric in a pluton for ‘normal’ rates (10⁻¹⁵ to 10⁻¹³ s⁻¹) of tectonic deformation.     

Deciphering the Variscan tectonothermal overprint and deformation partitioning in the Cadomian basement of the Teplá–Barrandian unit, Bohemian Massif

The Teplá–Barrandian unit (TBU) has long been considered as a simply bivergent supracrustal ‘median massif’ above the Saxothuringian subduction zone in the Variscan orogenic belt. This contribution reveals a much more complex style of the Variscan tectonometamorphic overprint and resulting architecture of the Neoproterozoic basement of the TBU. For the first time, we describe the crustal-scale NE–SW-trending dextral transpressional Krakovec shear zone (KSZ) that intersects the TBU and thrusts its higher grade northwestern portion severely reworked by Variscan deformation over a southeastern very low grade portion with well-preserved Cadomian structures and only brittle Variscan deformation. The age of movements along the KSZ is inferred as Late Devonian (~380–370?Ma). On the basis of structural, microstructural, and anisotropy of magnetic susceptibility data from the KSZ, we propose a new synthetic model for the deformation partitioning in the Teplá–Barrandian upper crust in response to the Late Devonian to early Carboniferous subduction and underthrusting of the Saxothuringan lithosphere. We conclude that the Saxothuringian/Teplá–Barrandian convergence was nearly frontal during ~380–346?Ma and was partitioned into pure shear dominated domains that accommodated orogen-perpendicular shortening alternating with orogen-parallel high-strain domains that accommodated dextral transpression or bilateral extrusion. The synconvergent shortening of the TBU was terminated by a rapid gravity-driven collapse of the thickened lithosphere at ~346–337?Ma followed by, or partly simultaneous with, dextral strike-slip along the Baltica margin-parallel zones, driven by the westward movement of Gondwana from approximately 345?Ma onwards.     

Assessing precision and accuracy of atmospheric emission inventories

Assuming that state-of-the-art air quality models are accurate, then the precision and accuracy of their results directly depend on the precision and accuracy of their geographical, meteorological and emission input data. There are important applications, such as open pit mining, in which emission data are the main source of uncertainty. In such cases, historical air quality experimental data are typically available. The present work proposes a backward air quality simulation approach to assess the accuracy of emission inventories for these applications, with the goal of identifying sources that are over or underestimated. This approach consists of finding constants of the linear combination of the estimated emission that maximize R ² and make the slope equal to one in the linear correlation analysis when the results from the air quality model are compared to the experimental measurements of air quality. This methodology was applied to the case of the mining region in northern Colombia. As one of the largest open pit coal mining regions in the world, this region consists of seven independent mines with no relevant additional sources of emission. Use of the proposed methodology allowed quantification of the amount by which companies over or underestimated their emission, as well as quantification of uncertainties due to sources not considered in the model but that locally affect each monitoring station.     

Implications of chloride-enhanced cadmium uptake in saline agriculture: modeling cadmium uptake by maize and tobacco

Chloride salinity has been strongly related to enhanced cadmium (Cd) uptake by plants due to increased solubility in the soil solution, even in agricultural soil with very low levels of cadmium. This finding is relevant because the cadmium content of food crops is an important concern for human health. Therefore, the aim of this study was to predict and discuss the chlorine-enhanced uptake of cadmium by two common crops: maize and tobacco under ??non-saline?? (1?mM) and ??very strongly saline?? (200?mM) scenarios using a modified ??biotic ligand model?? and datasets from a set of soil and hydroponic experiments. Results indicated that predicted cadmium uptake rates (expressed as cadmium in plant ??mol?m^?2 root) by maize and tobacco plants were consistently higher (54 and 15%, respectively) assuming conditions of ??very strong salinity?? soil compared to the simulated ??non-saline?? soil. In the light of the results of the present research, valuable information is given on modeled cadmium phytoavailability as an indication of the potential risk due to increased cadmium uptake by crops under saline conditions, especially as the enhancement of cadmium uptake in the presence of Cl^? salinity may be a general trend that occurs in many edible crops. The biotic ligand model parameterization applied in the present study attempted to simulate conditions commonly found in natural cadmium and salt-affected soils. However, caution is needed to extrapolate results obtained from these models to real soil conditions.     

Wavelet analysis of Fuenmayor karst spring,San Julián de Banzo,Huesca, Spain

Fuenmayor spring has been monitored continuously for identification purposes to study the behavior of a karst groundwater system. This paper initially deals with linear methods employing system engineering techniques for the analysis and identification of a hydrological system, considered as a black box model, which disregards information on the internal structure of the aquifer. Under a linear time invariant hypothesis, the application of the simple correlation of spectral analysis and parametric identification of transfer function generated some interesting results in the monitored spring. These tools have historically been successful in studying a large number of karst springs and continue to be practical approximations in initial attempts to obtain a draft model. Because of the nonlinear and nonstationary nature of karst, more effective systemic techniques are required to cover certain aspects of analysis that the linear system cannot reveal adequately. This paper presents interesting results using Fuenmayor spring data, collected over almost 10 years, to show the ability of wavelet techniques in the identification of a karst spring system.     

Geochemistry and health aspects of F-rich mountainous streams and groundwaters from sierras Pampeanas de Cordoba,Argentina

Symptoms of dental fluorosis have been observed in rural communities located in the Sierras Pampeanas de Córdoba, a mountainous area in Central Argentina. The clinical assessment was performed in the Charbonier Department, where the fluoride (F⁻) intake was determined to be 3.90 ± 0.20 mg day⁻¹ (n = 16). In this community, mild and severe fluorosis reach an incidence of 86.7% (total teeth surface = 636 teeth) among the children population. To determine the origin and distribution of fluorine in natural waters from the Charbonier Department and nearby regions, sampling was performed in the area covering the San Marcos River basin. The obtained results show that F⁻ concentrations vary between ~1 to ~2.5 mg l⁻¹, with an outlier value of 8 mg l⁻¹. The spatial distribution of F⁻ shows that the lowest concentrations are found at the basin’s catchments. Maximum values are located in two sectors of the basin: the Charbonier depression in the eastern part and at the San Marcos village, downstream the main collector, in the western part of the basin. In these two regions, the F⁻ contents in ground- and surface waters are >2.0 mg l⁻¹ and nearly constant. Dissolved F⁻ in natural waters from the study area has its origin in the weathering of F-bearing minerals present in the region’s dominant lithology. The extent of mineral weathering is mostly determined by the residence time of water within the aquatic reservoir. Longer residence times and a major solid–water interaction lead to enhanced release of F⁻. This explains the higher F⁻ concentrations found in basin areas with lower run off. The removal of F⁻ from water appears to occur by neither fluorite precipitation, nor by adsorption. Hence, variations in F⁻ concentrations seem to be more related to regional hydrological conditions.     

Hydrogeochemistry of fluoride in the Quequen river basin: natural pollutants distribution in the argentine pampa

Fluoride pollution is a widespread problem in Argentina, as it is in many areas of the World. Former investigations have demonstrated that the dissolution of volcanic glass disseminated in the loess-like sediments is the main source of fluoride in the Argentine pampas. Nevertheless, fluoride distribution is erratic and the factors controlling it are not yet well-known. A large amount of hydrochemical data collected in the Quequen Grande river catchment is used in order to contribute to the understanding of fluoride distribution and mobility in groundwater in the Argentine pampas. The Quequen Grande river catchment is 10,000 km². It extends between two low hills ranges of Precambrian metamorphic rocks and sedimentary Paleozoic rocks, filled by a thick sequence of Cenozoic sediments, mainly silts and silt-clayed, with sand layers. These sediments form a multilayer phreatic aquifer, which is recharged from precipitation infiltration, discharging through streams directly into the sea. Fluoride concentration in surface water (n = 353) ranges between 0 and 6.5 mg/l, with an average value of 2.14 mg/l. Groundwater concentration (n = 135) is from 0 up to 5.7 mg/l, with an average of 1.84 mg/l. Considering the statistic distribution of fluoride, two groups of samples can be determined. A dominant group between 0 and 3 mg/l, with a mean value around 1.5 mg/l, corresponding to samples widely distributed in the catchment; and a second one group with fluoride contents between 3 and 6 mg/l, corresponding to a smaller area in the central-west border. Two different sources are proposed. Volcanic glass dissolution is responsible for dominant values in the catchment, while the weathering of biotite from the Paleozoic bedrock can be assumed to account for the higher concentrations in the second group.     

Sources and behavior of arsenic and trace elements in groundwater and surface water in the Poopó Lake Basin,Bolivian Altiplano

Water management in semiarid and arid catchments such as the Poopó Lake Basin requires improved understanding of the complex behavior of the various contaminants, which affect the drinking water quality and considered as crucial for sustainable development of the region. Mechanisms of arsenic (As) release in the surface and groundwater were studied. Hydrochemical data for surface water (4 samples) and groundwater (28 samples) were collected in a small watershed in the Poopó catchment at the highland of the Bolivian Andes (Altiplano). All of them show high electrical conductivity values and moderately oxidizing conditions. The surface water contains high concentration of sulfate and the trace elements As, Zn and Pb in the zone affected by acid mine drainage. There is a large variability of the concentration of As and of the trace elements in the groundwater in the five different regions within the Poopó catchment. The metal concentrations sensitive to changes of redox state and results of speciation modeling suggest that As (V) is a predominant aqueous species, which conforms to the prevailing oxidizing conditions in the shallow groundwater environment. Two generalized trends for As distribution were identified in groundwater: (a) high concentrations are found in the arid zone (100–250 μg/L) in the southern (region III) and in the northwestern (region V) regions, and (b) low concentrations (<50 μg/L) are found in the remaining part of the basin (region I, II and IV). However, the spatial distribution within these regions needs to be investigated further. A conclusion from the present study is that there are multiple sources of As as well as other trace elements (such as Cd, Mn and Zn) in the Poopó Lake Basin. Among the sources and the processes which led to the mobility of As and other trace metals in the region are: (a) weathering of sulfide minerals, (b) oxidation of pyrite and/or arsenopyrite in mineralized areas and (c) desorption from hydrous ferric oxide (HFO) surfaces. In non-mining areas, volcanic ash is suggested to be a significant source of As.