Landscape variations in stream water SO4 and δSSO4 in a boreal stream network

Despite reduced anthropogenic deposition during the last decades, deposition sulphate may still play an important role in the biogeochemical cycles of S and many catchments may act as net sources of S that may remain for several decades. The aim of this study is to elucidate the temporal and spatial dynamics of both SO₄²⁻ and δ³⁴S_SO4 in stream water from catchments with varying percentage of wetland and forest coverage and to determine their relative importance for catchment losses of S. Stream water samples were collected from 15 subcatchments ranging in size from 3 to 6780 ha, in a boreal stream network, northern Sweden. In forested catchments (<2% wetland cover) S-SO₄²⁻ concentrations in stream water averaged 1.7 mg L⁻¹ whereas in wetland dominated catchments (>30% wetland cover) the concentrations averaged 0.3 mg L⁻¹. A significant negative relationship was observed between S-SO₄²⁻ and percentage wetland coverage (r² = 0.77, p < 0.001) and the annual export of stream water SO₄²⁻ and wetland coverage (r² = 0.76, p < 0.001). The percentage forest coverage was on the other hand positively related to stream water SO₄²⁻ concentrations and the annual export of stream water SO₄²⁻ (r² = 0.77 and r² = 0.79, respectively). The annual average δ³⁴S_SO4 value in wetland dominated streams was +7.6‰ and in streams of forested catchments +6.7‰. At spring flood the δ³⁴S_SO4 values decreased in all streams by 1‰ to 5‰. The δ³⁴S_SO4 values in all streams were higher than the δ³⁴S_SO4 value of +4.7‰ in precipitation (snow). The export of S ranged from 0.5 kg S ha⁻¹ yr⁻¹ (wetland headwater stream) to 3.8 kg S ha⁻¹ yr⁻¹ (forested headwater stream). With an average S deposition in open field of 1.3 kg S ha⁻¹ yr⁻¹ (2002-2006) the mass balance results in a net export of S from all catchments, except in catchments with >30% wetland. The high temporal and spatial resolution of this study demonstrates that the reducing environments of wetlands play a key role for the biogeochemistry of S in boreal landscapes and are net sinks of S. Forested areas, on the other hand were net sources of S.     

9: Processes of tectonism, magmatism and mineralization: Lessons from Europe

Metallogenic provinces in Europe range in age from the Archaean to the Neogene. Deposit types include porphyry copper and epithermal Cu–Au, volcanic-hosted massive sulphide (VMS), orogenic gold, Fe-oxide–Cu–Au, anorthosite Fe–Ti-oxide and sediment-hosted base-metal deposits. Most of them formed during short-lived magmatic events in a wide range of tectonic settings; many can be related to specific tectonic processes such as subduction, hinge retreat, accretion of island arcs, continental collision, lithosphere delamination or slab tear. In contrast, most sediment-hosted deposits in Europe evolved in extensional, continental settings over significant periods of time. In Europe, as elsewhere, ore formation is an integral part of the geodynamic evolution of the Earth's crust and mantle. Many tectonic settings create conditions conducive to the generation of water-rich magma, but the generation of ore deposits appears to be restricted to locations and short periods of change in temperature and stress, imposed by transitory plate motions. Crustal influence is evident in the strong structural controls on the location and morphology of many ore deposits in Europe. Crustal-scale fault–fracture systems, many involving strike-slip elements, have provided the fabric for major plumbing systems. Rapid uplift, as in metamorphic core complexes, and hydraulic fracturing can generate or focus magmatic–hydrothermal fluid flow that may be active for time spans significantly less than a million years. Once a hydrologically stable flow is established, ore formation is strongly dependent on the steep temperature and pressure gradients experienced by the fluid, particularly within the upper crust. In Europe, significant fracture porosity deep in the crystalline basement (1%) is not only important for magmatic–hydrothermal systems, but allows brines to circulate down through sedimentary basins and then episodically upward, expelled seismically to produce sediment-hosted base-metal deposits and Kupferschiefer copper deposits. Emerging research, stimulated by GEODE, can improve the predicting power of numerical simulations of ore-forming processes and help discover the presence of orebodies beneath barren overburden.     

A review on missing hydrological data processing

Like almost all fields of science, hydrology has benefited to a large extent from the tremendous improvements in scientific instruments that are able to collect long-time data series and an increase in available computational power and storage capabilities over the last decades. Many model applications and statistical analyses (e.g., extreme value analysis) are based on these time series. Consequently, the quality and the completeness of these time series are essential. Preprocessing of raw data sets by filling data gaps is thus a necessary procedure. Several interpolation techniques with different complexity are available ranging from rather simple to extremely challenging approaches. In this paper, various imputation methods available to the hydrological researchers are reviewed with regard to their suitability for filling gaps in the context of solving hydrological questions. The methodological approaches include arithmetic mean imputation, principal component analysis, regression-based methods and multiple imputation methods. In particular, autoregressive conditional heteroscedasticity (ARCH) models which originate from finance and econometrics will be discussed regarding their applicability to data series characterized by non-constant volatility and heteroscedasticity in hydrological contexts. The review shows that methodological advances driven by other fields of research bear relevance for a more intensive use of these methods in hydrology. Up to now, the hydrological community has paid little attention to the imputation ability of time series models in general and ARCH models in particular.     

Contrasting sources of Late Paleozoic rhyolite magma in the Polish Lowlands: evidence from U–Pb ages and Hf and O isotope composition in zircon

International Journal of Earth Sciences - The Polish Lowlands, located southwest of the Teisseyre–Tornquist Zone, within Trans-European Suture Zone, were affected by bimodal, but dominantly...     

Shale basins,sulfur-deficient ore brines and the formation of exhalative base metal deposits

The massive sulfide deposits of the Iberian Pyrite Belt are interbedded with felsic volcanic rocks and shale, and underlain by several thousand meters of siliciclastic sedimentary rocks known as the PQ Group. Isotope geochemistry and regional geology are both consistent with equilibration of the ore-forming fluids with the PQ Group, prior to ore deposition near the former seafloor. The average Cu:Zn:Pb ratio of the PQ Group rocks (ca. 26:55:19) is similar to the weighted average of all the massive sulfide orebodies combined (ca. 25:52:23).The genetic relationship between massive sulfide deposits and a siliciclastic sedimentary metal source is explained here by a thermodynamic model, proposing that mildly reducing redox conditions imposed by equilibration with the sedimentary rocks are most critical for the formation of an effective ore-forming fluid. Relatively metal-rich but organic-poor pyrite-bearing shale undergoing dewatering of saline pore fluids is an effective source for the generation of sulfur-deficient but relatively iron and base metal-rich brines. Thus, we propose that the giant deposits of the Iberian Pyrite Belt owe their existence not to exceptionally metal-enriched (e.g., magmatic) fluids, but to the existence of a fairly ordinary but large metal source in reactive siliciclastic sediments, combined with an underlying igneous heat source and a particularly efficient mechanism of sulfide precipitation by mixing with H₂S-rich fluids at or near the seafloor.Essentially similar mineral equilibria are imposed when saline fluids are buffered by typical continental basement rocks. Leaching of retrograde minerals and possibly residual salts from their magmatic or metamorphic prehistory is expected to generate similar, variably metal-rich but relatively sulfide-deficient fluids. Thus, the existence of mildly reducing rocks can be the dominant chemical control in the source of fluids generating many volcanogenic, Irish-type or sedex deposits, many of which are known to precipitate their metal load in response to biogenic sulfide addition at the ore deposition site.     

Identifying low-temperature hydrothermal karst and palaeowaters using stable isotopes: a case study from an alpine cave,Entrische Kirche,Austria

The area south of the prominent east–west trending Salzach Valley at the northern rim of the Central Alps of Austria has long been known to host anomalously warm springs emerging from a highly deformed calcite marble (Klammkalk). This unit also hosts cavities whose shapes suggest a hydrothermal karst origin and which are lined by calcite spar. We report here petrographic and isotopic evidence suggesting that dissolution by ascending low-temperature thermal waters also played an important role in the origin of a large cave in this region, Entrische Kirche. A paleo cave wall, preserved behind a thick flowstone in the interior of this cave, revealed a brownish bleaching zone which contrasts to the medium grey colour of the unaltered marble beneath. Across this zone the C and O isotope values gradually decrease by 3 and 11‰, respectively. These compositions are very different from those of the speleothem above but are similar to phreatic calcite spar from hydrothermal karst cavities in other outcrops in the area, where the absence of two-phase fluid inclusions suggests a low-temperature (less than ca. 50°C) hydrothermal origin. U/Th dating of the flowstone capping the alteration zone yielded a minimum age of the thermal water invasion in Entrische Kirche of ca. 240 kyr. There is no evidence in Entrische Kirche that these palaeowaters reached the point of calcite precipitation, but it is physically conceivable that higher and as yet unexplored parts of this deep (ca. 900 m) cave contain cavities lined by phreatic cave spar.     

Mapping the hydraulic connection between a coalbed and adjacent aquifer: example of the coal-seam gas resource area,north Galilee Basin,Australia

Coal-seam gas production requires groundwater extraction from coal-bearing formations to reduce the hydraulic pressure and improve gas recovery. In layered sedimentary basins, the coalbeds are often separated from freshwater aquifers by low-permeability aquitards. However, hydraulic connection between the coalbed and aquifers is possible due to the heterogeneity in the aquitard such as the existence of conductive faults or sandy channel deposits. For coal-seam gas extraction operations, it is desirable to identify areas in a basin where the probability of hydraulic connection between the coalbed and aquifers is low in order to avoid unnecessary loss of groundwater from aquifers and gas production problems. A connection indicator, the groundwater age indictor (GAI), is proposed, to quantify the degree of hydraulic connection. The spatial distribution of GAI can indicate the optimum positions for gas/water extraction in the coalbed. Depressurizing the coalbed at locations with a low GAI would result in little or no interaction with the aquifer when compared to the other positions. The concept of GAI is validated on synthetic cases and is then applied to the north Galilee Basin, Australia, to assess the degree of hydraulic connection between the Aramac Coal Measure and the water-bearing formations in the Great Artesian Basin, which are separated by an aquitard, the Betts Creek Beds. It is found that the GAI is higher in the western part of the basin, indicating a higher risk to depressurization of the coalbed in this region due to the strong hydraulic connection between the coalbed and the overlying aquifer.     

Neoproterozoic calc‐alkaline peraluminous granitoids of the Deleihimmi pluton,Central Eastern Desert,Egypt: implications for transition from late‐ to post‐collisional tectonomagmatic evolution in the northern Arabian–Nubian Shield

The widely distributed late‐collisional calc‐alkaline granitoids in the northern Arabian–Nubian Shield (ANS) have a geodynamic interest as they represent significant addition of material into the ANS juvenile crust in a short time interval (∼630–590 Ma). The Deleihimmi granitoids in the Egyptian Central Eastern Desert are, therefore, particularly interesting since they form a multiphase pluton composed largely of late‐collisional biotite granitoids enclosing granodiorite microgranular enclaves and intruded by leuco‐ and muscovite granites. Geochemically, different granitoid phases share some features and distinctly vary in others. They display slightly peraluminous (ASI = 1–1.16), non‐alkaline (calc‐alkaline and highly fractionated calc‐alkaline), I‐type affinities. Both biotite granitoids and leucogranites show similar rare earth element (REE) patterns [(La/Lu)_N = 3.04–2.92 and 1.9–1.14; Eu/Eu* = 0.26–0.19 and 0.11–0.08, respectively) and related most likely by closed system crystal fractionation of a common parent. On the other hand, the late phase muscovite granites have distinctive geochemical features typical of rare‐metal granites. They are remarkably depleted in Sr and Ba (4–35 and 13–18 ppm, respectively), and enriched in Rb (381–473 ppm) and many rare metals. Moreover, their REE patterns show a tetrad effect (TE_1,3 = 1.13 and 1.29) and pronounced negative Eu anomalies (Eu/Eu* = 0.07 and 0.08), implying extensive open system fractionation via fluid–rock interaction during the magmatic stage. Origin of the calc‐alkaline granitoids by high degree of partial melting of mafic lower crust with subsequent crystal fractionation is advocated. The broad distribution of late‐collisional calc‐alkaline granitoids in the northern ANS is related most likely to large areal and intensive lithospheric delamination subsequent to slab break‐off and crustal/mantle thickening. Such delamination caused both crustal uplift and partial melting of the remaining mantle lithosphere in response to asthenospheric uprise. The melts produced underplate the lower crust to promote its melting. The presence of microgranular enclaves, resulting from mingling of mantle‐derived mafic magma with felsic crustal‐derived liquid, favours this process. The derivation of the late‐phase rare‐metal granites by open system fractionation via fluid interaction is almost related to the onset of extension above the rising asthenosphere that results in mantle degassing during the switch to post‐collisional stage. Consequently, the switch from late‐ to post‐collisional stage of crustal evolution in the northern ANS could be potentially significant not only geodynamically but also economically. Copyright © 2011 John Wiley & Sons, Ltd.     

Probability Density Functions as Botanical-Climatological Transfer Functions for Climate Reconstruction

We present a new procedure, the pdf method (pdf=probability density function), for reconstructing Quaternary climate utilizing botanical data. The procedure includes the advantages of the indicator species method by considering the fossil and modern presence and absence of taxa rather than their frequencies, thus avoiding the need for modern analog plant communities. Overcoming the problematic use of absolute limits to describe climate response ranges is the main progress of the pdf method in comparison to the indicator species method. This advantage results from estimating probability density functions (pdfs) for monthly mean January and July temperature conditional on the present day occurrence of single taxa. Gaussian distributions sufficiently approximate pdfs of many, although not all, studied taxa. On the assumption of statistical independence, the procedure calculates a joint pdf as the product of the pdfs of the individual taxa. This algorithm weights each taxon according to the extent of its climate response range expressed by its covariance structure. We interpret the maximum of the resulting pdf as the most likely climate and its confidence interval as the uncertainty range. To avoid an artificial reduction of uncertainty arising from the use of numerous similar pdfs, a preselection method is proposed based on the Mahalanobis distance between pdfs. The pdf method was applied to the Carpinus phase of a profile from Gröbern, Germany, that spans the last interglaciation (Eemian). The reconstructed most probable January and July temperatures of about 0.0°C and 18.4°C barely differ from the modern values of −0.5°C and 18.3°C.