Inter‐laboratory Characterisation of Apatite Reference Materials for Chlorine Isotope Analysis

Here we report on a set of six apatite reference materials (chlorapatites MGMH#133648, TUBAF#38 and fluorapatites MGMH#128441A, TUBAF#37, 40, 50) which we have characterised for their chlorine isotope ratios; these RMs span a range of Cl mass fractions within the apatite Ca₁₀(PO₄)₆(F,Cl,OH)₂ solid solution series. Numerous apatite specimens, obtained from mineralogical collections, were initially screened for ³⁷Cl/³⁵Cl homogeneity using SIMS followed by δ³⁷Cl characterisation by gas source mass spectrometry using both dual‐inlet and continuous‐flow modes. We also report major and key trace element compositions as determined by EPMA. The repeatability of our SIMS results was better than ± 0.10‰ (1s) for the five samples with > 0.5 % m/m Cl and ± 0.19‰ (1s) for the low Cl abundance material (0.27% m/m). We also observed a small, but significant crystal orientation effect of 0.38‰ between the mean ³⁷Cl/³⁵Cl ratios measured on three oriented apatite fragments. Furthermore, the results of GS‐IRMS analyses show small but systematic offset of δ³⁷Cl_SMOC values between the three laboratories. Nonetheless, all studied samples have comparable chlorine isotope compositions, with mean 10³δ³⁷Cl_SMOC values between +0.09 and +0.42 and in all cases with 1s ≤ ± 0.25.     

Temporal evolution of backward erosion piping in small-scale experiments

Backward erosion piping (BEP) is a form of internal erosion which can lead to failure of levees and dams. Most research focused on the critical head difference at which piping failure occurs. Two aspects have received less attention, namely (1) the temporal evolution of piping and (2) the local hydraulic conditions in the pipe and at the pipe tip. We present small-scale experiments with local pressure measurements in the pipe during equilibrium and pipe progression for different sands and degrees of hydraulic loading. The experiments confirm a positive relation between progression rate and grain size as well as the degree of hydraulic overloading. Furthermore, the analysis of local hydraulic conditions shows that the rate of BEP progression can be better explained by the bed shear stress and sediment transport in the pipe than by the seepage velocity at the pipe tip. The experiments show how different processes contribute to the piping process and these insights provide a first empirical basis for modeling pipe development using coupled seepage-sediment transport equations.

     

Gefüge und Entstehung der Ringdünen in den grauen Tuffen des Laacher Vulkans

The last products of the pleistocene Laach volcano (Eifel, about 40 kms SW of Bonn, Germany) are grey tuffs. Outcrops in the rim show characteristic cross-bedding in these tuffs. It is in discussion whether these structures are produced by wind or by phreato-magmatic outbursts. At all larger outcrops in the rim we measured numerous depositional elements of the tuffs, and analyzed their geometrical structure. So we are able to reconstruct shape, structure and orientation of dunes in the tuffs. They show transport vectors in centrifugal orientation, radially to the vent. The dunes are orientated concentrically to the vent, we intruduce the term “concentrical dune” for this dune type. This points out that the dunes in the Laach tuffs are of volcanic origin. But our geometrical results give no authorization to assume phreato-magmatic processes during the activity of the Laach volcano. We think that the grey Laach tuffs are no base surge deposits, but products of gas-rich eruptions in the phase of decreasing volcanic energy.     

Mid-Paleocene event at Gabal Nezzazat,Sinai, Egypt: planktonic foraminiferal biostratigraphy,mineralogy and geochemistry

The Qreiya Beds that record the ‘mid-Paleocene event’ at Gabal Nezzazat occur within the Igorina albeari (P3b) Zone and constitute part of a 14-m thick shale succession that ranges in age from Early to Late Paleocene. They are composed of four alternating dark grey and brown shale beds, which are thinly laminated, phosphatic, organic-rich and extremely sulphidic. They are characterized by distinct enrichment and high peak anomalies in chalcophiles (Zn, Co, Ni, Cu and Pb) and organic association elements (V and Cr), especially within the brown organic-rich beds. It is concluded that these elements are incorporated into the phosphatic debris, sulphides and organic matter. In contrast, the grey beds are enriched in clay minerals and quartz. Clay mineral assemblages indicate alternating periods of warm/humid climate (high kaolinite) and dry climate (low kaolinite) during the formation of the grey and brown beds, respectively. The sediments of the Qreiya Beds yield lithological, biotic, geochemical and mineralogical data indicative of suboxic/anoxic marine environments as a result of high productivity and/or upwelling. The top metre of the succession below the Qreiya Beds is characterized by a progressive change from faunas dominated by praemurcurids to faunas dominated by Morozovilids, and by a progressive upward decrease in δ¹³C_carb and δ¹⁸O_carb values. The foraminiferal faunal change may reflect shallowing and warming preceding deposition of the Qreiya Beds. The change in isotopic values is inferred to be the result of surface weathering, fluvial input and diagenesis with no evidence of any primary change that could support presence of a hyperthermal event.     

Evolution of a hydrothermal fluid-rock interaction system as recorded by Sr isotopes: A case study from the Schwarzwald, SW Germany

Metasomatic and Sr-isotopic changes, associated with formation of zoned alteration halos along hydrothermal veins, are documented for a gneiss from the Artenberg quarry near Steinach (Kinzigtal, Schwarzwald, SW Germany). Veins are postorogenic, SW-NE-oriented, and cut straight through metaquartzdioritic Variscan gneiss, where flow of low-temperature fluids (～100–200°C) caused adularia-quartz-sericite-type alteration. Fluid-rock interaction occurred nearly 50 Ma after Variscan metamorphism, as constrained by a Rb–Sr multimineral isochron for unaltered gneiss of 327.1?±?3.1 Ma, and by two independent ages of 279.2?±?3.1 Ma and 274?±?13 Ma, based on Rb–Sr systematics of late-stage quartz from the veins. In a profile from unaltered gneiss towards a vein, alteration-induced mineralogical changes correlate with metasomatic net addition of K, Rb, and Cl to the alteration zone, combined with net loss of Na, Ca, and Sr. Strontium isotopes give a more detailed insight into the fluid-rock interaction process. ⁸⁷Sr/⁸⁶Sr ratios in a profile across the alteration zone are incompatible with simple Sr leaching but reflect partial replacement of the rocks’ Sr by fluid-derived Sr, the isotopic composition of which varied with time. Early fluids, with high ⁸⁷Sr/⁸⁶Sr ratios compared to unaltered gneiss, evolved into fluids with somewhat lower ratios, and finally reached a second maximum in ⁸⁷Sr/⁸⁶Sr ratios. This Sr-isotopic fluid evolution is equally revealed by the mineral sequence of the vein mineralization. It appears that the compositional evolution of the fluids correlates with the sequence of mineral breakdown reactions in the gneissic host rock, and that the Sr-isotopic evolution of the fluids can be fully explained as the result of internal, progressive reaction of fluid with the local rocks. Results also show that the spatial distributions of Sr isotopes in metasomatic alteration zones may reflect the complex evolution of fluid-rock interaction systems, and ultimately constrain the factors controlling both fluid compositions and alteration patterns.     

Holocene peatland development and hydrological variability inferred from bog‐pine dendrochronology and peat stratigraphy – a case study from southern Sweden

Dendrochronological analysis was applied to subfossil remains of Scots pine (Pinus sylvestris L.) buried in a South Swedish peat deposit. In combination with peat stratigraphy, this approach was explored for its potential to provide information on the local hydrological and depositional history at the site, forming the basis for a regional palaeohydrological analysis. A 726‐year ring‐width chronology was developed and assigned an absolute age of 7233–6508 cal a BP (5284–4559 BC) through cross‐dating with German bog‐pine chronologies, whereas two short additional records of older ages were radiocarbon dated. Registration of growth positions of individual trees allowed assessment of the spatial dynamics of the pine population in response to hydrological changes and peatland ontogeny. Annually resolved growth variability patterns in the pine population reveal several establishment and degeneration phases, probably reflecting fluctuations in bog‐surface wetness. A major establishment phase at 7200–6900 cal a BP reflects the onset of a period of lowered groundwater level, also indicated by increased peat humification, and a development consistent with regional temperature and lake level reconstructions revealed from other proxies. This study demonstrates that subfossil bog‐pine populations may provide annually to decadally resolved reconstructions of local groundwater variability, which are highly relevant in a long‐term palaeoclimatic context. Copyright © 2012 John Wiley & Sons, Ltd.     

Carry-over effects of the membrane interface probe

The membrane interface probe (MIP) is widely used to characterize the subsurface distribution of volatile organic compounds (VOCs). One problem that arises during MIP application is that disproportionately high MIP signals are obtained after passing source zones which contain mobile or residual phases. This serious problem occurs because of a carry-over effect, in particular caused by compound-specific retention times in the conventional unheated transfer line, commonly used during such an investigation. The objective of this study was to perform a qualitative methodical field evaluation of the carry-over effect of a conventional MIP system with a conventional unheated transfer line. This was achieved by coupling a mobile mass spectrometer to the MIP device. Results obtained were then further compared with those achieved using a laser induced fluorescence (LIF) system. Because of this coupling, time- and depth-dependent signals for different substances became known. Field evaluation data obtained showed complex superpositions of compounds with MIP system results. As a result of this superposition, MIP signals from the saturated zone beneath the source zone (zone with free and/or residual phase) are blurred and are therefore not representative of particular depths. However, utilizing multidirectional probing alongside conventional MIP probing (forwards and backwards), it was possible to detect the upper and lower phase boundary of the source zone. These MIP results correlated excellently with the LIF results. An important conclusion that can be drawn from the field investigation is that coupling a mobile mass spectrometer to the MIP system enables advanced MIP signal interpretation to be successfully achieved.