Quantification of karst aquifer discharge components during storm events through end-member mixing analysis using natural chemistry and stable isotopes as tracers

Karst aquifer components that contribute to the discharge of a water supply well in the Classical Karst (Kras) region (Italy/Slovenia) were quantitatively estimated during storm events. Results show that water released from storage within the epikarst may comprise as much as two-thirds of conduit flow in a karst aquifer following rainfall. Principal components analysis (PCA) and end-member mixing analysis (EMMA) were performed using major ion chemistry and the stable isotopes of water (δ¹⁸O, δ²H) and of dissolved inorganic carbon (δ¹³C_DIC) to estimate mixing proportions among three sources: (1) allogenic river recharge, (2) autogenic recharge, and (3) an anthropogenic component stored within the epikarst. The sinking river most influences the chemical composition of the water-supply well under low-flow conditions; however, this proportion changes rapidly during recharge events. Autogenic recharge water, released from shallow storage in the epikarst, displaces the river water and is observed at the well within hours after the onset of precipitation. The autogenic recharge end member is the second largest component of the well chemistry, and its contribution increases with higher flow. An anthropogenic component derived from epikarstic storage also impacts the well under conditions of elevated hydraulic head, accounting for the majority of the chemical response at the well during the wettest conditions.     

Geochronological constraints on the Legs Lake shear zone with implications for regional exhumation of lower continental crust, western Churchill Province, Canadian Shield

The Legs Lake shear zone marks the southeastern boundary of an extensive region (>20,000 km²) of high-pressure (0.8–1.5+ GPa) granulite-facies rocks in the western Churchill Province, Canada. The shear zone is one of the largest exhumation-related structures in the Canadian Shield and coincides with the central segment of the ∼2,800 km long Snowbird tectonic zone. The movement history of this shear zone is critical for the development of models for the exhumation history of the high-pressure region. We used electron microprobe U–Th–Pb dating of monazite with supplemental ID-TIMS U–Pb geochronology to place constraints on the timing of shear zone activity. Combining these and other data, we suggest that regional exhumation occurred during at least three distinct phases over an ∼150 million year period. The first phase involved high temperature decompression from ∼1.0 to 0.8–0.7 GPa shortly following 1.9 Ga peak metamorphism, possibly under an extensional regime. The second phase involved rock uplift and decompression of the hanging wall to 0.5–0.4 GPa during east-vergent thrusting across the Legs Lake shear zone at ca. 1.85 Ga. This phase was likely driven by early collision-related convergence in the Trans-Hudson orogen. The final phase of regional exhumation, involving the removal of 15–20 km of overburden from both footwall and hanging wall, likely occurred after ∼1.78 Ga and may have been related to regional extensional faulting.Electronic Supplementary Material Supplementary material is available to authorised users in the online version of this article at .     

Timescales and significance of high-pressure, high-temperature metamorphism and mafic dike anatexis, Snowbird tectonic zone, Canada

New geochronological, isotopic and geochemical data for a spectacular swarm of deep crustal migmatitic mafic dikes offer important insight into processes operative during 1.9 Ga high pressure, high temperature metamorphism along the Snowbird tectonic zone in northern Saskatchewan. High-precision U–Pb zircon dates reveal anatexis of Chipman mafic dikes at 1,896.2 ± 0.3 Ma during syntectonic and synmetamorphic intrusion at conditions of 1.0–1.2 GPa, >750°C. U–Pb zircon dates of 1,894–1,891 Ma for cross-cutting pegmatites place a lower bound on major metamorphism and deformation at the currently exposed crustal levels. The persistence of elevated temperatures for ~14 m.y. following peak conditions is implied by younger U–Pb titanite dates, and by Sm–Nd whole rock isotopic data that suggest the derivation of the pegmatites by melting of a mafic source. Limited melting of the host felsic gneiss at 1.9 Ga despite high temperature is consistent with evidence for their previous dehydration by granulite facies metamorphism in the Archean. Spatial heterogeneity in patterns of mafic dike and tonalitic gneiss anatexis can be attributed to lateral peak temperature and compositional variability. We correlate 1,896 Ma Chipman mafic dike emplacement and metamorphism with substantial 1.9 Ga mafic magmatism over a minimum along-strike extent of 1,200 km of the Snowbird tectonic zone. This suggests a significant, continent-wide period of asthenospheric upwelling that induced incipient continental rifting. Extension was subsequently terminated by hinterland contraction associated with Trans-Hudson accretion and orogenesis. Little activity in the lower crust for ca. 650 m.y. prior to Proterozoic metamorphism and mafic magmatism implies an extended interval of cratonic stability that was disrupted at 1.9 Ga. This episode of destabilization contrasts with the record of long-term stability in most preserved cratons, and is important for understanding the lithospheric characteristics and tectonic circumstances that control the destruction or survival of continents.     

Synchrotron IR study of hydrous ringwoodite (γ-Mg2SiO4) up to 30 GPa

High-pressure synchrotron infrared (IR) absorption spectra were collected between 650 and 4,000 cm⁻¹ at ambient temperature for hydrous Mg-ringwoodite (γ-Mg₂SiO₄) up to 30 GPa. The main feature in the OH⁻ stretching region is an extremely broad band centred at 3,150 cm⁻¹. The hydrogen bond is strong for most protons and the most probable site for protonation is the tetrahedral edge. With increasing pressure, this band shifts downward while decreasing its integrated intensity until disappearance at a pressure of 25 GPa. Only one band at 2,450 cm⁻¹ and an absorption plateau persist with a maximum wavenumber of 3,800 cm⁻¹. This behaviour is reversible upon pressure release. We interpret this as a second-order phase transition occurring in hydrated Mg-ringwoodite at high pressure (beyond ∼ 25 GPa). This result is compatible with the observation by Kleppe et al. (Phys Chem Miner 29:473–476, 2002a) who suggested the presence of Si–O–Si linkages and/or partial increase in the coordination of Si. Beyond the phase transition, the protons are delocalized and their environment on the ringwoodite structure is probably quite different from that at low pressure. Data obtained in situ at high pressures and temperatures are needed to better understand the effect of protonation on the structure and to better constrain this phase transition.     

Spatial process and data models: Toward integration of agent-based models and GIS

The use of object-orientation for both spatial data and spatial process models facilitates their integration, which can allow exploration and explanation of spatial-temporal phenomena. In order to better understand how tight coupling might proceed and to evaluate the possible functional and efficiency gains from such a tight coupling, we identify four key relationships affecting how geographic data (fields and objects) and agent-based process models can interact: identity, causal, temporal and topological. We discuss approaches to implementing tight integration, focusing on a middleware approach that links existing GIS and ABM development platforms, and illustrate the need and approaches with example agent-based models.     

The negative alpha filter: a new Processing technique for polarimetric SAR interferometry

In this letter we develop a new concept, the negative alpha filter, which we suggest has application for quantitative estimation of surface parameters beneath vegetation using polarimetric synthetic aperture radar (SAR) interferometry (POLInSAR). We first derive the filter and then validate it using simulations of L-band coherent forest scattering. We then show initial results of applying the filter to airborne data from the German Aerospace Center's E-SAR L-band sensor.     

Up to what temperature is petroleum stable? New insights from a 5200 free radical reactions model

The discovery of crude oils and condensates at ever higher temperatures casts doubt on the validity of the usual geochemical modelling approach, that uses empirical reactions and rate constants. The solution used to account for such a high thermal stability is presently to adjust the rate parameters, but the physical meaning and scientific value of such a strategy can be questioned. We have developed a mechanistic model consisting of 5200 lumped free radical reactions to describe the thermal evolution of a mixture of 52 organic species meant to represent light petroleum. Rate constants used are those available in the literature or estimated using well established thermochemistry-reactivity correlations. Chemical structures included in the model are linear, branched and cyclic hydrocarbons, hydro- and alkyl-aromatics, PAHs, and three heteroatomic compounds. Reactions include cracking and alkylation chains and inhibiting and accelerating reactions from the various reactants. This model has been applied to several mixtures with various proportions of reaction inhibitors and accelerators, and to a composition representing a light mature oil. From the results obtained, we conclude that mature oils will be stable up to 240–260 °C, depending on their composition, and that the thermal cracking of oil to gas is not possible under reasonable basin conditions. The kinetics of petroleum cracking are thus much slower than generally recognized.     

Anhydrite-bearing rocks from the Rožná district (Moldanubian zone,Czech Republic): high-grade metamorphosed exhalites?

Several types of anhydrite-bearing rocks have been found in the amphibolite-facies metamorphosed rocks at the north-eastern margin of the Moldanubian Zone. Anhydrite either forms monomineralic bands up to 40 cm thick, or occurs in the form of disseminated grains in surrounding calc-silicate gneiss together with feldspar, scapolite, amphibole, pyroxene, epidote and pyrite. The isotopic composition of sulphur ('³⁴S=30.6 to 32.3‰) and strontium (⁸⁷Sr/⁸⁶Sr=0.70797 to 0.70781) in anhydrite may indicate a marine source of sulphate. The isotopic ratio of strontium is in the same range as that of metamorphosed strata-bound barite-sulphide ores, which have been previously described in the same area. The '³⁴S values of coexisting pyrite range from 21.4 to 22.5‰, the (³⁴S_{anhydrite-pyrite} corresponding to the metamorphic temperature of 600 to 660 °C. In contrast to many submarine-exhalative deposits, the oxygen isotopic compositions of anhydrite ('¹⁸O=9.3 to 10.2‰) are lighter than that of barite ('¹⁸O=10.4 to 13.8‰). This indicates that the both minerals are not in isotopic equilibrium. Therefore, it is probable that anhydrite and barite from the Ro—ná district were deposited from fluids that contained different proportions of seawater and hydrothermal fluids or from hydrothermal fluids that underwent variable extent of oxygen isotope exchange with seafloor rocks. The '¹³C values in calcite ('¹³C=-17.2 to -18.7‰) from anhydrite-bearing rock are lower than those in distant marbles. As graphite is absent in anhydrite- and calcite-bearing rocks, impoverishment in the ¹³C isotope cannot be attributed to the graphite-carbonate isotopic exchange during metamorphism. It is proposed that low '¹³C values in carbonates are caused by pre-metamorphic oxidation of organic matter in course of hydrothermal processes. Anhydrite and anhydrite-bearing calc-silicate gneiss from the north-eastern part of the Moldanubian Zone are interpreted to be the high-grade metamorphosed analogue of anhydrite-rich exhalites commonly found in submarine-exhalative hydrothermal deposits.