Moldavites from the Cheb Basin, Czech Republic

Between 1993 and 2007, an estimated 2500-3000 individual moldavite pieces have been found in the Tertiary Cheb Basin, Western Bohemia. This identifies the area as the third most prominent source of Central European tektites, next to the South Bohemian and West Moravian strewn subfields. Basic macroscopic physical properties (weight, shape, color and sculpture) were evaluated for over 350 individual finds of tektites from 4 different localities in the Cheb Basin. All these properties are similar to those observed for the South Bohemian moldavites, particularly with respect of color and weight distribution. In total, 24 tektites from the Cheb Basin have been characterized chemically using electron microprobe. For comparison, a set of 17 moldavites from the South-Bohemian and Moravian strewn subfields was measured as well. Contents of major elements overlap between the two sample sets; the largest variation was observed for iron. The trends observed in the Harker plots, however, seem to differentiate several partial subgroups, some of them characteristic for Cheb tektites only. These results are also substantiated by cluster analysis, which reveals a tight group for most of the tektites from the Cheb Basin, forming two partial clusters. The rest of the Cheb moldavites cluster with the South Bohemian samples. Minor and trace elements were measured with an LA-ICP-MS technique; CI-normalized REE patterns compare well with those for other moldavites. Many tektites, both from Cheb and South Bohemia or Moravia, display considerable heterogeneity: they frequently show schlieren and fluidal fabric. Two samples of this kind from the Cheb Basin showed considerable enrichment in volatile elements (e.g., Zn and Cu), which is typical for Muong Nong-type Australasian tektites. Mössbauer spectroscopy confirmed the highly reducing character of 5 studied moldavites. Discovery of a new moldavite strewn subfield around Cheb substantiates the theory that moldavites were ejected from the Ries impact structure in a fan-shaped jet, although it is not clear yet if it was continuous or composed of individual rays. In addition, the chemistry of the Cheb moldavites indicates significant precursor material heterogeneity.     

Documentary proxies and interdisciplinary research on historic geomorphologic hazards: a discussion of the current state from a central European perspective

During the last two decades, documentary data (written and iconographic sources) have been increasingly employed in geomorphologic research aiming at reconstruction of territorial distribution, temporal occurrence and social and economic impacts of various geomorphologic hazards. The goal of this paper is to broaden the previous discussion (Glade et al. The use of historical data in natural hazard assessments. Kluwer, Dordrecht, 2001) of the methodological constraints on the use of documentary data for geomorphologic hazard research. Using the interdisciplinary approach of geomorphology, historiography and medial studies, we firstly summarise the major finding of papers that have employed various types of documentary data sources to study geomorphologic hazards in different regions. In the second section, we present case studies from the Czech Republic resulting from the ongoing research project that is devoted to the assessment of the potential of documentary data to reconstruct past occurrences of and mitigation strategies for geomorphologic hazards. Finally, we discuss three main methodological issues emerging from our research: (a) problems emerging from the positivist approach to documentary data sources and the necessity for critical analyses of documentary data sources based on modern historiographic approaches, (b) constraints arising from the combination of documentary data from different spatiotemporal scales and (c) lacks in the use of documentary data to study local-based adaptation strategies to cope with geomorphologic hazards.     

Effects of melt percolation on highly siderophile elements and Os isotopes in subcontinental lithospheric mantle: A study of the upper mantle profile beneath Central Europe

The effects of melt percolation on highly siderophile element (HSE) concentrations and Re-Os isotopic systematics of subcontinental lithospheric mantle are examined for a suite of spinel peridotite xenoliths from the 4 Ma Kozákov volcano, Bohemian Massif, Czech Republic. The xenoliths have previously been estimated to originate from depths ranging from ∼32 to 70 km and represent a layered upper mantle profile. Prior petrographic and lithophile trace element data for the xenoliths indicate that they were variably modified via metasomatism resulting from the percolation of basaltic melt derived from the asthenosphere. Chemical and isotopic data suggest that lower sections of the upper mantle profile interacted with melt characterized by a primitive, S-undersaturated composition at high melt/rock ratios. The middle and upper layers of the profile were modified by more evolved melt at moderate to low melt/rock ratios. This profile permits an unusual opportunity to examine the effects of variable melt percolation on HSE abundances and Os isotopes.Most HSE concentrations in the studied rocks are significantly depleted compared to estimates for the primitive upper mantle. The depletions, which are most pronounced for Os, Ir and Ru in the lower sections of the mantle profile, are coupled with strong HSE fractionations (e.g., Os_N/Ir_N ratios ranging from 0.3 to 2.4). Platinum appears to have been removed from some rocks, and enriched in others. This enrichment is coupled with lithophile element evidence for the degree of percolating melt fractionation (i.e., Ce/Tb ratio).Osmium isotopic compositions vary considerably from subchondritic to approximately chondritic (γ_Os at 5 Ma from -6.9 to +2.1). The absence of correlations between ¹⁸⁷Os/¹⁸⁸Os and indicators of fertility, as is common in many lithospheric mantle suites, may suggest significant perturbation of the Os isotopic compositions of some of these rocks, but more likely reflect the normal range of isotopic compositions found in the modern convecting mantle. Osmium isotopic compositions correspondingly yield model Re-depletion (T_RD) ages that range from essentially modern to ∼1.3 Ga.Our data provide evidence for large-scale incompatible behavior of HSE during melt percolation as a result of sulfide dissolution, consistent with observations of prior studies. The degree of incompatibility evidently depended on melt/rock ratios and the degree of S-saturation of the percolating melt. The high Pt contents of some of these rocks suggest that the Pt present in this pervasively metasomatized mantle was controlled by a phase unique to the other HSE. Further, high Os concentrations in several samples suggest deposition of Os in a minority of the samples by melt percolation. In these rocks, the mobilized Os was characterized by similar to the ¹⁸⁷Os/¹⁸⁸Os ratios in the ambient rocks. There is no evidence for either the addition of Os with a strongly depleted isotopic composition, or Os with suprachondritic isotopic composition, as is commonly observed under such circumstances.     

Determination of Trace Elements in Calcite Using Solution and Laser Ablation ICP-MS: Calibration to NIST SRM Glass and USGS MACS Carbonate, and Application to Real Landfill Calcite

We report new data on the trace element concentrations of Mg, Cr, Mn, Co, Ni, Cu, Zn, Sr, Cd, Ba, La, Ce, Nd, Pb and U in USGS carbonate reference materials (MACS-1 and MACS-2) and compare solution ICP-MS and LA-ICP-MS trace element determinations on landfill calcites using calibration to different reference materials (MACS-1 and MACS-2 carbonate and NIST SRM 612 glass). Very good agreement (differences below 10% relative) was found between laser ablation and solution ICP-MS data for MACS-1 with higher concentrations of trace elements (values between 100 and 150 μg g⁻¹), with the exception of Cu and Zn. Similarly good agreement was found for MACS-2 with lower trace element concentrations (units to tens of μg g⁻¹), with the exception of Cr, Co and Zn. The MACS-1 reference material for calibration of LA-ICP-MS was found to be extremely useful for in situ determination of trace elements in real-world carbonate samples (landfill calcites), especially those present in calcite in higher concentrations (Mn, Sr, Ba; < 5% RSD). Less accurate determinations were generally obtained for trace elements present at low concentrations (∼ units of μg g⁻¹). In addition, good agreement was observed between the instrument calibration to MACS and NIST SRM 612 glass for in situ measurements of trace elements in landfill calcites K-2, K-3 and K-4 (differences below 15% relative for most elements). Thus, the application of MACS carbonate reference materials is promising and points to the need for the development of new carbonate reference materials for laser ablation ICP-MS.     

Laser Ablation and Solution ICP-MS Determination of Rare Earth Elements in USGS BIR-1G, BHVO-2G and BCR-2G Glass Reference Materials

Data are reported for rare earth elements (REE) in three geological glass reference materials (BIR-1G, BHVO-2G and BCR-2G) using a UV (266 nm) laser ablation ICP-MS system and the classical (HF-HClO₄) acid decomposition method, followed by conventional nebulisation ICP-MS. External calibration of laser ablation analyses was performed using NIST SRM reference materials with internal standardisation using ²⁹Si and ⁴⁴Ca. Replicate analyses of reference basaltic glasses yielded an analytical precision of 1-5% (RSD) for all the elements by solution ICP-MS and 1-8% (RSD) by laser ablation ICP-MS. The relative differences between the REE concentrations measured by solution and laser ablation ICP-MS compared with the reference values were generally less than 11 % for most elements. The largest deviations occurred for La determined by solution ICP-MS in BIR-1G. The results of both solution and laser ablation ICP-MS agreed well, generally better than 7%, with the exception of La, Pr and Sm in BIR-1G. The measured REE laser ablation data for BIR-1G, BHVO-2G and BCR-2G agreed with the previously published data on these basaltic reference glasses, within a range of 0-10% for most elements. No significant influences were observed for the predicted spectral interferences on some REE isotopes in the analysis of basaltic glasses.     

Removal of trace elements from landfill leachate by calcite precipitation

Spontaneous precipitation of secondary calcite (CaCO₃) has been observed in 25 samples of landfill leachate-polluted stream waters. During the 6-month precipitation experiment, the formation of calcite acts as a principal trace-element scavenging process. The concentrations of Fe, Sr, Ba and Mn and other trace elements in solution significantly decreased as calcite formed during the experiments. The PHREEQC-2 geochemical code indicated high supersaturation of the initial leachate-polluted waters with respect to calcite. The chemical/mineralogical study (SEM/EDS, XRD, ICP MS) revealed that this newly formed calcite contains considerable amounts of metals and metalloids removed from solution. Such a geochemical process can be considered to be important for spontaneous decontamination in landfill-affected environments (stream sediments, soils) or landfill technical facilities (settling basins). This removal takes place especially during dry periods with low rain precipitation, when the landfill waters exhibit both higher alkalinity and higher trace element concentrations.     

Sedimentary provenance of Mid-Devonian clastic sediments in the Teplá-Barrandian Unit (Bohemian Massif): U–Pb and Pb–Pb geochronology of detrital zircons by laser ablation ICP-MS

Summary The provenance of the Mid-Devonian clastic sediments in the Teplá-Barrandian Unit (TBU) of the Bohemian Massif was investigated by laser ablation ICP-MS U–Pb zircon dating, bulk sediment geochemistry and mineralogical study of the heavy mineral fraction. In contrast to the island arc provenance of the TBU Neoproterozoic sediments, the Early Palaeozoic sediments contain significant amounts of differentiated crustal material. The detrital zircon populations in the Barrandian Mid-Devonian siltstones and sandstones show ages ranging from Archaean (3.0Ga) to Early Palaeozoic (0.39Ga). Major age maxima are at 2.6Ga, 2.0–2.25Ga, 0.62 and 0.51Ga. The youngest identified zircons so far correspond to Lower and Mid-Devonian ages. The extensive mechanical abrasion of zircons having Archaean (3.0, 2.8 and 2.6Ga) to Paleoproterozoic ages (2.25–2.0Ga) suggest their provenance from recycled old sedimentary sequences. The relatively large number of zircons with ages between 2.0 and 3.0Ga may indicate the presence of relicts of the Archaean/Paleoproterozoic crust in the source areas of the studied Mid-Devonian sediments. The absence of detrital zircon ages between 0.9 and 1.2Ga and the presence of zircon ages of 2.0–2.25 and 0.5–0.8Ga correspond to the zircon age pattern from the Gondwana-related North African, rather than Gondwana-related South American and Baltic terranes. The material was entering the basin predominantly from the west and consisted primarily of detrital material of Cambrian granitoids and recycled material of Neoproterozoic meta-sedimentary sequences.     

Determination of Gold in e‐Waste Dust Samples and Geological Matrices by ICP‐MS after Extraction by an HClO4‐HBr‐HI‐Aqua Regia Mixture

This study describes two methods (Procedures‐1 and ‐2) for the direct extraction of Au by an inorganic acid mixture (HClO₄‐HBr‐HI‐aqua regia) from complex sample matrices. Standard PTFE jars at 200 °C were used to decompose test portions of 0.5–1 g, with subsequent precise and accurate analysis by ICP‐MS without any other preconcentration or separation. Procedure‐1 decomposed samples effectively without the necessity of leaching with HF and was developed for dust samples from e‐waste (electronic waste) processing; however, testing on geological reference materials showed very good results. The analyses of replicate decompositions (n = 5) from both procedures yielded very good precision (< 5% RSD) for most of the reference materials. The accuracy achieved was better than ± 10%, with the exception of NIST SRM 2782 data from Procedure‐1. Two unknown samples of dust from e‐waste processing (P‐1 and VM‐1) exhibited elevated concentrations of Au (21.31–61.64 μg g^?1) with precision better than 10% (n = 5). The proposed techniques are simple, sensitive and sparing in the use of chemicals, and are designed for a variety of e‐waste dust samples. No significant influences were observed for the predicted spectral interferences on mass ¹⁹⁷Au.     

Lead Isotopic Composition in Biogenic Certified Reference Materials Determined by Different ICP‐based Mass Spectrometric Techniques

This work presents data for the radiogenic Pb isotopic ratios (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb) in nine biogenic certified reference materials (NIST SRM 1515, 1566b, 1570a, 1573a, 1575a; BCR 100, BCR 101, BCR 670 and IAEA 359), which are suitable for analytical quality control in environmental research. The results were obtained using three different types of ICP‐based mass spectrometer (quadrupole‐based/magnetic sector field single‐collector ICP‐MS instruments and a multi‐collector ICP‐MS) and applying different mass bias correction procedures (calibrator‐sample bracketing and external Tl normalisation) with and without Pb separation from the matrix using ion exchange chromatography. In the majority of the samples, the measurements from all three of the ICP‐MS instruments were in agreement within ± 0.1%, despite the lower analytical precision of the single‐collector ICP‐MS instruments. We demonstrate that the presence of the sample matrix did not significantly influence the Pb isotopic ratios measured by magnetic sector field ICP‐MS, whereas the use of the two different mass bias corrections resulted in a systematic difference of 0.09% for the ²⁰⁸Pb/²⁰⁶Pb ratio.