Water source characterization through spatiotemporal patterns of major,minor and trace element stream concentrations in a complex,mesoscale German catchment

The link between spatiotemporal patterns of stream water chemistry and catchment characteristics for the mesoscale Dill catchment (692 km²) in Germany is explored to assess the catchment scale controls on water quality and to characterize water sources. In order to record the spatiotemporal pattern, ‘snapshot sampling’ was applied during low, mean and high flow, including 73 nested sites throughout the catchment. Water samples were analysed for the elements Li, B, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Mo, Ba, Pb and U using inductively‐coupled‐plasma mass spectrometry, and for electric conductivity and pH. Principle component analysis and hierarchical cluster analysis were used to find typical element associations and to group water samples according to their hydrochemical fingerprints. This revealed regional hydrochemical patterns of water quality which were subsequently related to catchment attributes to draw conclusions about the controls on stream chemistry. It was found that various lithologic signals and anthropogenic point source inputs controlled the base flow hydrochemistry. During increased flows, stream waters were diluted causing additional hydrochemical variability in response to heterogeneous precipitation inputs and differences in aquifer storage capacities. The hydrochemical patterns further displayed in‐stream mixing of waters. This implied, that stream waters could be apportioned to the identified water sources throughout the catchment. The basin‐wide hydrochemical variability has the potential to outrange the tracer signatures typically inferred in studies at the hillslope scale and is able to strongly influence the complexity of the catchment output. Both have to be considered for further catchment scale tracer and modelling work. Despite the likelihood of non‐conservative behaviour, the minor and trace elements enhanced the rather qualitative discrimination of the various groundwater types, as the major cations were strongly masked by point source inputs. Copyright © 2007 John Wiley & Sons, Ltd.     

Submarine hydrothermal activity and gold-rich mineralization at Brothers Volcano, Kermadec Arc, New Zealand

Brothers volcano, of the Kermadec intraoceanic arc, is host to a hydrothermal system unique among seafloor hydrothermal systems known anywhere in the world. It has two distinct vent fields, known as the NW Caldera and Cone sites, whose geology, permeability, vent fluid compositions, mineralogy, and ore-forming conditions are in stark contrast to each other. The NW Caldera site strikes for ??600?m in a SW?CNE direction with chimneys occurring over a ??145-m depth interval, between ??1,690 and 1,545?m. At least 100 dead and active sulfide chimney spires occur in this field and are typically 2?C3?m in height, with some reaching 6?C7?m. Their ages (at time of sampling) fall broadly into three groups: <4, 23, and 35?years old. The chimneys typically occur near the base of individual fault-controlled benches on the caldera wall, striking in lines orthogonal to the slopes. Rarer are massive sulfide crusts 2?C3?m thick. Two main types of chimney predominate: Cu-rich (up to 28.5?wt.% Cu) and, more commonly, Zn-rich (up to 43.8?wt.% Zn). Geochemical results show that Mo, Bi, Co, Se, Sn, and Au (up to 91?ppm) are correlated with the Cu mineralization, whereas Cd, Hg, Sb, Ag, and As are associated with the dominant Zn-rich mineralization. The Cone site comprises the Upper Cone site atop the summit of the recent (main) dacite cone and the Lower Cone site that straddles the summit of an older, smaller, more degraded dacite cone on the NE flank of the main cone. Huge volumes of diffuse venting are seen at the Lower Cone site, in contrast to venting at both the Upper Cone and NW Caldera sites. Individual vents are marked by low-relief (??0.5?m) mounds comprising predominately native sulfur with bacterial mats. Vent fluids of the NW Caldera field are focused, hot (??300°C), acidic (pH????2.8), metal-rich, and gas-poor. Calculated end-member fluids from NW Caldera vents indicate that phase separation has occurred, with Cl values ranging from 93% to 137% of seawater values. By contrast, vent fluids at the Cone site are diffuse, noticeably cooler (??122°C), more acidic (pH?1.9), metal-poor, and gas-rich. Higher-than-seawater values of SO₄ and Mg in the Cone vent fluids show that these ions are being added to the hydrothermal fluid and are not being depleted via normal water/rock interactions. Iron oxide crusts 3?years in age cover the main cone summit and appear to have formed from Fe-rich brines. Evidence for magmatic contributions to the hydrothermal system at Brothers includes: high concentrations of dissolved CO₂ (e.g., 206?mM/kg at the Cone site); high CO₂/³He; negative ??D and ??¹⁸O_H2O for vent fluids; negative ??³⁴S for sulfides (to ?4.6??), sulfur (to ?10.2??), and ??¹⁵N₂ (to ?3.5??); vent fluid pH values to 1.9; and mineral assemblages common to high-sulfidation systems. Changing physicochemical conditions at the Brothers hydrothermal system, and especially the Cone site, occur over periods of months to hundreds of years, as shown by interlayered Cu?+?Au- and Zn-rich zones in chimneys, variable fluid and isotopic compositions, similar shifts in ³He/⁴He values for both Cone and NW Caldera sites, and overprinting of ??magmatic?? mineral assemblages by water/rock-dominated assemblages. Metals, especially Cu and possibly Au, may be entering the hydrothermal system via the dissolution of metal-rich glasses. They are then transported rapidly up into the system via magmatic volatiles utilizing vertical (??2.5?km long), narrow (??300-m diameter) ??pipes,?? consistent with evidence of vent fluids forming at relatively shallow depths. The NW Caldera and Cone sites are considered to represent stages along a continuum between water/rock- and magmatic/hydrothermal-dominated end-members.     

<Superscript>57</Superscript>Fe Mössbauer spectroscopy,X-ray single-crystal diffractometry,and electronic structure calculations on natural alexandrite

Natural alexandrite Al₂BeO₄:Cr from Malyshevo near Terem Tschanka, Sverdlovsk, Ural, Russia, has been characterized by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine oxidation state and location of iron. The sample contains 0.3 wt% of total iron oxide. The ⁵⁷Fe Mössbauer spectrum can be resolved into three doublets. Two of them with hyperfine parameters typical for octahedrally coordinated high-spin Fe³⁺ and Fe²⁺, respectively, are assigned to iron substituting for Al in the octahedral M2-site. The third doublet is attributed to Fe³⁺ in hematite. Electronic structure calculations in the local spin density approximation are in reasonable agreement with experimental data provided that expansion and/or distortion of the coordination octahedra are presumed upon iron substitution. The calculated hyperfine parameters of Fe³⁺ are almost identical for the M1 and M2 positions, but the calculated ligand-field splitting is by far too large for high-spin Fe³⁺ on M1.     

Comparison of CloudSat cloud liquid water paths in arctic summer using ground-based microwave radiometer

Arctic clouds strongly influence the regional radiation balance, temperature, melting of sea ice, and freezing of sea water. Despite their importance, there is a lack of systematic and reliable observations of Arctic clouds. The CloudSat satellite launched in 2006 with a 94 GHz Cloud Profiling Radar (CPR) may contribute to close this gap. Here we compare one of the key parameters, the cloud liquid water path (LWP) retrieved from CloudSat observations and from microwave radiometer (MWR) data taken during the ASCOS (Arctic Summer Cloud Ocean Study) cruise of the research vessel Oden from August to September 2008. Over the 45 days of the ASCOS cruise, collocations closer than 3 h and 100 km were found in only 9 d, and collocations closer than 1 h and 30 km in only 2 d. The poor correlations in the scatter plots of the two LWP retrievals can be explained by the patchiness of the cloud cover in these two days (August 5th and September 7th), as confirmed by coincident MODIS (Moderate-resolution Imaging Spectroradiometer) images. The averages of Oden-observed LWP values are systematically higher (40–70 g m⁻²) than the corresponding CloudSat observations (0–50 g m⁻²). These are cases of generally low LWP with presumably small droplets, and may be explained by the little sensitivity of the CPR to small droplets or by the surface clutter.     

On the occurrence and origin of anthropogenic radionuclides found in a fragment of the Chelyabinsk (LL5) meteorite

A piece of the 2013 Chelyabinsk meteorite was investigated for its content of anthropogenic radionuclides. In addition to traces of cesium‐137 that had been previously reported for this particular fragment, we found an unusually high amount of strontium‐90, which indicates that the source of this contamination was the Kyshtym accident (1957). A high Sr‐90/Cs‐137 activity ratio is characteristic for Kyshtym‐derived contaminations. Based on the cesium‐137 content in the soil from the finding site, it is estimated that the fragment was contaminated with soil particles in the milligram range upon impact. Investigation of the soil revealed very unusual ferromagnetic characteristics and an iron‐rich chemical composition. Mössbauer spectroscopy indicated the presence of steel components in this soil, suggesting that the investigated meteorite fragment was found in an industrial dumping site rather than natural soil.     

Unravelling the pre-Variscan evolution of the Habach terrane (Tauern Window, Austria) by U-Pb SHRIMP zircon data

The U-Pb SHRIMP age determinations of zircons from the Habach terrane (Tauern Window, Austria) reveal a complex evolution of this basement unit, which is exposed in the Penninic domain of the Alpine orogen. The oldest components are found in zircons of a metamorphosed granitoid clast, of a migmatitic leucosome, and of a meta-rhyolitic (Variscan) tuff which bear cores of Archean age. The U-Pb ages of discordant zircon cores of the same rocks range between 540 and 520 Ma. It is assumed that the latter zircons were originally also of Archean origin and suffered severe lead loss, whilst being incorporated into Early-Cambrian volcanic arc magmas. The provenance region of the Archean (2.64-2.06 Ga) zircons is assumed to be a terrane of Gondwana affinity: i.e., the West African craton (Hoggar Shield, Reguibat Shield). The Caledonian metamorphism left a pervasive structural imprint in amphibolite facies on rocks of the Habach terrane; it is postdated by discordant zircons of a migmatitic leucosome at <440 Ma (presumably ca. 420 Ma). Alpine and Variscan upper greenschist- to amphibolite-facies conditions caused partial lead loss in zircons of a muscovite gneiss ('white schist') only, where extensive fluid flow and brittle deformation due to its position near a nappe-sole thrust enhanced the grains' susceptibility to isotopic disturbance. The Habach terrane - an active continental margin with ensialic back-arc development - showed subduction-induced magmatic activity approx. between 550 and 507 Ma. Back-arc diorites and arc basalts were intruded by ultramafic sills and subsequently by small patches of mantle-dominated unaltered and (in the vicinity of a major tungsten deposit) altered granitoids. Fore-arc (shales) and back-arc (greywackes, cherts) basin sediments as well as arc and back-arc magmatites were not only nappe-stacked by the Caledonian compressional regime closing the presumably narrow oceanic back-arc basin and squeezing mafic to ultramafic cumulates out of high-level magma chambers (496-482 Ma). It also induced uplift and erosion of deeply rooted crystalline complexes and triggered the development of a successor basin filled with predominantly clastic greywacke-arkosic sediments. The study demonstrates that the basement rocks exposed in the Habach terrane might be the 'missing link' between similar units of the more westerly positioned External domain (i.e., Aar, Aiguilles Rouges, Mont Blanc) and the Austroalpine domain to the east (Oetztal, Silvretta).     

Palaeovariations in the East-Asian Monsoon Regime Geochemically Recorded in Varved Sediments of Lake Sihailongwan (Northeast China, Jilin Province). Part 1: Hydrological Conditions and Dust Flux

The varved sediments of the dimictic Lake Sihailongwan (Long Gang mountain area, Jilin Province, Northeast China) represent a palaeoclimatic archive which documents the local precipitation frequency during the summer monsoon, and variations in the aeolian flux of dust with their remote sources in the arid and semi-arid regions of inner Asia. Based on a detailed discussion of sediment genesis in Lake SHL, dust flux rates and palaeohydrological conditions were reconstructed on a decadal scale over the past 220 years. The aeolian influx by dry and wet deposition was quantified and characterised in its chemical composition. Photosynthetic production in the lake is positively correlated with the inflow of nutrient-rich groundwater. The groundwater discharge largely reflects the strength of the summer monsoon. Net accumulation rates for biogenic silica were determined for annually laminated sediments from the centre of the U-shaped lake basin based on sediment data. In a Si-balance model of the modern lake, the depositional flux of biogenic silica could be independently quantified on the base of hydrochemical monitoring data. Comparison of the both estimates allowed to asses the focussing of the particle flux in the lake. Though water retention in Lake SHL is rather high (ca. 30 years), changes in the hydrological conditions are sensitively recorded in the sediments because (i) nutrient-rich groundwater discharges into the productive zone of the lake, (ii) a substantial proportion of the total dissolved Si-inventory of the mixed lake (ca. 30%) is annually consumed by diatom growth, and (3) sediment accumulation is substantially focussed towards the flat bottom of the lake basin. The bulk siliciclastic sediment fraction (ca. 75 wt.%) largely originates from influx of dust of remote provenance. In sediment thin-sections, the dry-deposited dust fraction is microscopically identifiable as seasonal silt layer. Aeolian input by wet-deposition shows a distinctly higher variability than the influx of dust by dry-deposition. As diatom production, wet-deposition of dust is positively correlated with the rainfall during the summer monsoon. The inferred positive correlation between rainfall and dust flux during the summer monsoon implies that dust deposition is determined by the out-wash efficiency of mineral particles for a permanent high atmospheric dust concentration over Northeast China in the last 220 years.     

Numerical modeling of fracking fluid migration through fault zones and fractures in the North German Basin

Gas production from shale formations by hydraulic fracturing has raised concerns about the effects on the quality of fresh groundwater. The migration of injected fracking fluids towards the surface was investigated in the North German Basin, based on the known standard lithology. This included cases with natural preferential pathways such as permeable fault zones and fracture networks. Conservative assumptions were applied in the simulation of flow and mass transport triggered by a high pressure boundary of up to 50 MPa excess pressure. The results show no significant fluid migration for a case with undisturbed cap rocks and a maximum of 41 m vertical transport within a permeable fault zone during the pressurization. Open fractures, if present, strongly control the flow field and migration; here vertical transport of fracking fluids reaches up to 200 m during hydraulic fracturing simulation. Long-term transport of the injected water was simulated for 300 years. The fracking fluid rises vertically within the fault zone up to 485 m due to buoyancy. Progressively, it is transported horizontally into sandstone layers, following the natural groundwater flow direction. In the long-term, the injected fluids are diluted to minor concentrations. Despite the presence of permeable pathways, the injected fracking fluids in the reported model did not reach near-surface aquifers, either during the hydraulic fracturing or in the long term. Therefore, the probability of impacts on shallow groundwater by the rise of fracking fluids from a deep shale-gas formation through the geological underground to the surface is small.     

Development and validation of a finite element morphological model for shallow water basins

Recognising the importance of understanding sediment dynamics to evaluate the status of a coastal lagoon environment, this work has been focused on the investigation of the hydrodynamic and sediment transport processes occurring in such basins. In order to describe the lagoon system, a modelling approach combining hydrodynamics, waves and sediment dynamics has been developed. The framework of the numerical model consists of a finite element hydrodynamic model, a third generation finite element spectral wave model and a sediment transport and morphodynamic model for both cohesive and non-cohesive sediments. The model adopts the finite element technique for spatial integration, which has the advantage to describe more accurately complicated bathymetry and irregular boundaries for shallow water areas. The developed model has been applied to test cases and to a very shallow tidal lagoon, the Venice Lagoon, Italy. Numerical results show good agreement with water level, waves and turbidity measurements collected in several monitoring stations inside the Lagoon of Venice. Such a model represents an indispensable tool in analysing coastal problems and assessing morphological impacts of human interference.