The Early Palaeozoic Break-up of Northern Gondwana: Sedimentology, Physical Volcanology and Geochemistry of a Submarine Volcanic Complex in the Bavarian Facies Association, Saxothuringian Basin, Germany

Ordovician volcano-sedimentary successions of the Bavarian facies association in the Saxothuringian basin record the continental rift phase of the separation of the Saxothuringian Terrane from Gondwana. An 80 m succession from the Vogtendorf beds and Randschiefer Series (Arenig-Middle Ordovician), exposed along the northern margin of the Münchberg Gneiss Massif in northeast Bavaria, were subjected to a study of their sedimentology, physical volcanology and geochemistry. The Randschiefer series previously has been interpreted as lavas, tuffs, sandstones and turbidites, but the studied Ordovician units include four main lithological associations: mature sandstones and slates, pillowed alkali-basalts and derivative mass flow deposits, trachyandesitic lavas and submarine pyroclastic flow deposits interbedded with turbidites. Eight lithofacies have been distinguished based on relict sedimentary structures and textures, which indicate deposition on a continental shelf below wave base. The explosive phase that generated the pyroclastic succession was associated with the intrusion of dykes and sills, and was succeeded by the eruption of pillowed basalts. Debris flow deposits overlie the basalts. Ordovician volcanism in this region, therefore, alternated between effusive and explosive phases of submarine intermediate to mafic volcanism.

Based on geochemical data, the volcanic and pyroclastic rocks are classified as basalts and trachyandesites. According to their geochemical characteristics, especially to their variable concentrations of incompatible elements such as the High Field Strength Elements (HFSE), they can be divided into three groups. Group I, which is formed by massive lavas at the base of the succession, has extraordinarily high contents of HFSE. The magmas of this group were probably derived from a mantle source in the garnet stability field by low (ca. 1%) degrees of partial melting and subsequent fractionation. Group II, which comprises the pillow lavas at the top of the sequence, displays moderate enrichment of HFSE. This can be explained by a slightly higher degree of melting (ca. 1.6%) for the primary magma. Group I and II melts fractionated from their parental magmas in different magma chambers. The eruption centres of Groups I and II, therefore, cannot be the same, and the volcanic rocks must have originated from different vents. The sills and pyroclastic flow deposits of Group III stem at least partly from the same source as Group I. Rocks of Group I most likely mixed together with Group II components during the formation of the Group III flows, which became hybridised during eruption, transportation and emplacement.

The sedimentological and geochemical data best support a rift as the tectonic setting of this volcanism, analogous to modern continental rift zones. Hence, the rift-associated volcanic activity preserved in the Vogtendorf beds and Randschiefer Series represents an early Ordovician stage of rift volcanism when the separation of the Saxothuringian Terrane from Gondwana had just commenced.     

Trace element signature and U–Pb geochronology of eclogite-facies zircon,Bergen Arcs,Caledonides of W Norway

Secondary-ion mass spectrometry (SIMS) U–Pb and trace element data are reported for zircon to address the controversial geochronology of eclogite-facies metamorphism in the Lindås nappe, Bergen Arcs, Caledonides of W Norway. Caledonian eclogite-facies overprint in the nappe was controlled by fracturing and introduction of fluid in the Proterozoic—Sveconorwegian—granulite-facies meta-anorthosite-norite protolith. Zircon grains in one massive eclogite display a core–rim structure. Sveconorwegian cores have trace element signatures identical with those of zircon in the granulite protolith, i.e. 0.31Th/U0.89, heavy rare earth element (HREE) enrichment, and negative Eu anomaly. Weakly-zoned to euhedral oscillatory-zoned Caledonian rims are characterized by Th/U0.13, low LREE content (minimum normalized abundance for Pr or Nd), variable enrichment in HREE, and no Eu anomaly. A decrease of REE towards the outermost rim, especially HREE, is documented. This signature reflects co-precipitation of zircon with garnet and clinozoisite in a feldspar-absent assemblage, and consequently links zircon to the eclogite-facies overprint. The rims provide a mean ²⁰⁶Pb/²³⁸U crystallization age of 423±4 Ma. This age reflects eclogite-forming reactions and fluid–rock interaction. This age indicates that eclogite-facies overprint in the Lindås nappe took place at the onset of the Scandian (Silurian) collision between Laurentia and Baltica.     

Correlations and sequence stratigraphic model for Messinian carbonate platforms of the western and central Mediterranean

Distance correlations of Late Tortonian–Messinian littoral carbonate complexes are proposed from the study of eight platforms in the western and central Mediterranean. Correlations are based on the identification of two major biological sedimentary cycles and of two index surfaces. Surface A is a maximum flooding surface during cycle 1 at around 6.7 Ma. Surface B is a regional marine planation surface at around 5.95 Ma, at the base of cycle 2 (Terminal Carbonate Complex). A general sedimentary model is proposed for the 7–5.6-Ma time-span. The boundary between cycles 1 and 2 is coincident with the onset of the Messinian Salinity Crisis, and appears to be related to major environmental–paleo-oceanographic changes in the Mediterranean, rather than to a major sea-level drop or to climatic change.     

Spatial Association of Mineral Occurrences and Curvilinear Geological Features

Qualitative and quantitative knowledge about the spatial association between mineral occurrences and geological features are important in mineral potential mapping. Two existing methods for quantifying spatial association between mineral occurrences and curvilinear geological features are applied to the Baguio district of the Philippines. An experimental method is described and applied to the study area as well. The results of the three methods are highly similar, which demonstrates the effectiveness of the experimental method presented here for quantifying spatial association between mineral occurrences and curvilinear geological features. It is shown that gold occurrence in the Baguio district are strongly spatially associated with northeasterly trending faults/fractures rather than with northwesterly trending faults/fractures. It is also shown that the spatial association between the gold occurrence and older batholithic intrusives is stronger than the spatial association between gold occurrence and younger porphyry intrusives. These spatial geoinformation characteristics can be used as evidential data layers in GIS-based mineral potential mapping.     

Trace element mapping by LA-ICP-MS: assessing geochemical mobility in garnet

A persistent problem in the study of garnet geochemistry is that the consideration of major elements alone excludes a wealth of information preserved by trace elements, particularly the rare-earth elements (REEs). This is despite the fact that trace elements are generally less vulnerable to diffusive resetting, and are sensitive to a broader spectrum of geochemical interactions involving the entire mineral assemblage, including the growth and/or dissolution of accessory minerals. We outline a technique for the routine acquisition of high-resolution 2D trace element maps by LA-ICP-MS, and introduce an extension of the software package XMapTools for rapid processing of LA-ICP-MS data to visualise and interpret compositional zoning patterns. These methods form the basis for investigating the mechanisms controlling geochemical mobility in garnet, which are argued to be largely dependent on the interplay between element fractionation, mineral reactions and partitioning, and the length scales of intergranular transport. Samples from the Peaked Hill shear zone, Reynolds Range, central Australia, exhibit contrasting trace element distributions that can be linked to a detailed sequence of growth and dissolution events. Trace element mapping is thus employed to place garnet evolution in a specific paragenetic context and derive absolute age information by integration with existing U–Pb monazite and Sm–Nd garnet geochronology. Ultimately, the remarkable preservation of original growth zoning and its subtle modification by subsequent re-equilibration is used to ‘see through’ multiple superimposed events, thereby revealing a previously obscure petrological and temporal record of metamorphism, metasomatism, and deformation.     

Changing compositions in the Iceland plume; Isotopic and elemental constraints from the Paleogene Faroe flood basalts

Elemental and Sr, Nd, Hf and high precision Pb isotopic data are presented from 59 low-Ti and high-Ti lavas from the syn-break up part of the Faroe Flood Basalt Province. The depleted MORB-like low-Ti lavas erupted in the rift zone between the Faroe Islands and central East Greenland around the time of break up of the North Atlantic have isotopic end-member compositions different from the depleted Iceland lavas. We suggest that the main low-Ti mantle component is NAEM (North Atlantic End-Member (Ellam and Stuart, 2000, J. Petrol. 41, 919) and that the ²⁰⁷Pb/²⁰⁴Pb value of the component should be 15.35 and ε_Hf = + 16.5. NAEM is the main depleted component in the early Iceland plume. This is supported by high mantle potential temperatures (up to 1550 °C) calculated for the source of the low-Ti basalts. The unique mantle isotopic composition of NAEM with low ²⁰⁶Pb/²⁰⁴Pb (17.5) and Δ7/4Pb (? 3.8) precludes a derivation from recycled MORB lithosphere. Instead we suggest that NAEM represents a plume component of recycled depleted Archean lithospheric mantle that was further depleted ~ 500 Ma ago, possibly in connection with the recycling process. Two other isotopic end-members are required to explain the variation of the Faroe low-Ti basalts: (1) The Faroe depleted component (FDC), with ⁸⁷Sr/⁸⁶Sr = 0.7025, ε_Nd = + 11, ε_Hf = + 19.5, ²⁰⁶Pb/²⁰⁴Pb = 18.2, ²⁰⁷Pb/²⁰⁴Pb = 15.454 and ²⁰⁸Pb/²⁰⁴Pb = 37.75, which is similar in composition to some Atlantic MORB and is regarded as a local upper mantle source. (2) An enriched EM-type component similar in geochemistry to the Icelandic Öræfajökull lavas. This component is believed to be recycled pelagic sediments in the plume but it can alternatively be a local crustal or lithospheric mantle component. The enriched Faroe high-Ti lavas erupted inland from the rift have isotopic compositions very similar to the enriched Icelandic neo-volcanics and these lava suites apparently share the two enriched plume end-members IE1 and IE2 (Geochim. Cosmochim. Acta 68, 2, 2004). The lack of mixing between high and low-Ti melts at the time of break up, is explained by a zoned plume where only low-Ti sources were present beneath the rift zone surrounded by high-Ti sources on both sides of the rift. The enriched plume components in the high-Ti lava sequences on the Faroe Islands and central East Greenland changed rapidly on a ka-scale which implies, from geophysical modelling, that this area was positioned above the center of the plume, and that the Iceland plume was centered under the Atlantic ridge already from the Paleocene.     

Influence of subsolidus processes on the chromium number in spinel in ultramafic rocks

The chromium number of spinel Cr#^sp (atomic ratio of Cr/(Cr+Al)) is an important geochemical parameter for the estimation of the degree of partial melting, temperatures, and provenance in peridotites. In this study, a model has been developed in order to determine the effect of subsolidus reactions on the Cr#^sp in ultramafic rocks. The final model includes temperature-dependent distribution coefficients of relevant reactions as well as solubility data and has been applied to lithologies common in mid-ocean ridge settings. Significant changes in the Cr#^sp are predicted from the application of this model during cooling from 1300 to 800°C at mantle pressures. For spinel lherzolites and harzburgites, the Cr#^sp is predicted to decrease proportional to the absolute values of the Cr#^sp at (constantly) increasing spinel mass. Cpx-dunites show the same trend, although to a lower extent. Websterites show a different behavior with a slight increase in the Cr#^sp due to their lack of olivine. Modal abundance of spinel correlates with the magnitude in Cr#^sp change, too. Finally, these results were tested for possible effects on the calculated degree of partial melting as function of the Cr#^sp. Application of the Cr#^sp from a peridotite equilibrated down to 800°C would result in an underestimation of only 1.5 % in the degree of melting, justifying the use of Cr#^sp for estimations of this parameter.     

Seasonal variations of Zn, Cu, As and Mo in arsenic-rich stream at the Mokrsko gold deposit, Czech Republic

Monthly sampling of slightly alkaline arsenic-rich stream in the Mokrsko gold deposit revealed seasonal variations in dissolved Zn, Cu, As and Mo. Concentrations of trace metal cations (Zn, Cu) increased as much as 330 and 178%, respectively, from minimum mean values at autumn to maximum mean values at spring. In contrast, concentrations of trace element oxyanions (As, Mo) revealed opposite seasonal pattern with increase to 189% (As) and 123% (Mo) during summer–autumn, indicating that in-stream biogeochemical process(es) played the main role in controlling the seasonal variations of these trace elements. The trace elements were mainly scavenged by low crystalline Mn oxyhydroxide and Fe oxyhydroxide (ferrihydrite). Results are consistent with sorption and coprecipitation processes controlling seasonal variations of dissolved Zn and Cu, while As and Mo dynamics appear linked to Mn redox reactions. The sorption processes and Mn redox processes are attributed to the changes of pH and oxic/anoxic conditions on the surface of oxyhydroxides, respectively, which are themselves controlled by the balance between photosynthesis and respiration. Under the geochemical conditions of the stream, inferred Mn redox reactions can only be explained by microbial activity.     

Calcium isotope constraints on the uptake and sources of Ca in a base-poor forest: A new concept of combining stable (δCa) and radiogenic (εCa) signals

Plant-available reserves of major base cations, Ca²⁺ and Mg²⁺, decreased markedly in soils over the past century, thus posing a potential threat to forest ecosystem health. Trees are thought to obtain dissolved Ca²⁺ ions mainly from an easily accessible soil-water reservoir also termed the ‘exchangeable cation pool’. The status of Ca reserves in this soil pool is sensitive to anthropogenic perturbations such as soil acidification induced by acid rain and/or excessive timber harvesting. Here we show that in a base-poor forest of the northeastern USA (i.e. Wachusett Mountain, Massachusetts) the ‘exchangeable Ca pool’ of deeper mineral soils has a unique isotope signature that is significantly enriched in the radiogenic ⁴⁰Ca, due to the dissolution of K-rich silicate minerals such as biotite. Using a simple isotope mass balance, and assuming that the input of Ca from biotite has a ε_Ca signature of ∼16, the results of our calculation indicate that the weathering of biotite may supply a sizeable fraction, up to 25%, of Ca²⁺ ions into the ‘exchangeable cation pool’ of deeper mineral soils. Importantly, samples of local vegetation (i.e. woody tissues of red oak) show no detectable excess of the radiogenic ⁴⁰Ca, and based on our model the upper limit of a possible biotite-derived Ca contribution in vegetation is estimated at ∼5%. We also found no evidence of the radiogenic ⁴⁰Ca signal in the samples of forest floor and the uppermost organic-rich soils (0-15 cm depth), which in turn suggest that over the long-term development of the forest and its organic matter accumulation, the vegetation growth must have also relied primarily on the non-radiogenic Ca sources. Based on our experimental data, such sources may include (i) wet atmospheric deposition, (ii) the organically-complexed Ca in topsoil horizons, and (iii) chemical weathering and/or fungal-mediated dissolution of apatite and Ca-rich plagioclase. Hence, our stable and radiogenic Ca isotope data indicate that the studied base-poor forest is able to bypass the ‘exchangeable cation pool’ of deeper (i.e. below 15 cm) mineral soils, and still manages to meet its nutritional requirements with respect to Ca. Another important implication of this study is that the organically-complexed Ca in the topsoil horizon (0-15 cm depth) has to be tightly bound to the ion exchange sites, otherwise the large radiogenic ⁴⁰Ca signatures present in the ‘exchangeable cation pool’ of deep mineral soils would be swamped by the downward gravitational flux of non-radiogenic Ca from the decaying organic matter and litterfall. Hence, the limited mobility of the organically-complexed Ca in soils and its tight biological cycling could explain the lack of a significant impact of vegetation on the Ca isotope systematics observed in large rivers.