Rare earth, major and trace elements in Jurassic manganese shales of the Northern Calcareous Alps: hydrothermal versus hydrogenous origin of stratiform manganese deposits

Summary ?The rare earth, major and trace element geochemistry of Jurassic deep marine manganese shales allow insight into their environment of deposition. We present data of 24 samples from the Northern Calcareous Alps (Eastern Alps), collected from Late Jurassic strata of the Tennengebirge and from Early Jurassic strata of the Karwendel Mts. Whereas major and trace element geochemistry is controlled by the detrital input, rare earth element data and the relationship between total organic carbon and (pyritic) sulfur can be used to constrain the origin of the manganese accumulation. The data of this study are compatible with a hydrogenous precipitation of manganese by strongly varying redox-conditions at the sediment–water interface of a slope basin. Received December 21, 2001; revised version accepted February 18, 2002     

Reply to Aikin and Underwood

A list of continuum windows in umbral spectra is given and briefly discussed.     

International Association of Geoanalysts' Protocol for the Certification of Geological and Environmental Reference Materials: A Supplement

The International Association of Geoanalysts (IAG) published a protocol for the certification of reference materials in close accord with the International Organisation for Standardisation (ISO) guidelines (Kane et al. 2003). This article supplements that protocol, providing additional discussion of best approaches for pre-selecting laboratories for participation in certification projects. This discussion also makes a distinction between inter-laboratory certifications, where n = 15 is the general standard, and expert laboratory certifications, where a much smaller number of laboratories will be deemed qualified to provide data of the quality needed for certification.     

Petrology of Al- and Cr-rich ophiolitic chromitites from the Muğla,SW Turkey: implications from composition of chromite,solid inclusions of platinum-group mineral,silicate, and base-metal mineral,and Os-isotope geochemistry

Ultramafic rocks around the city of Muğla in SW Turkey are represented by mantle peridotites depleted to various degrees, ranging from cpx-rich harzburgites to depleted harzburgite and dunite. Cpx-rich harzburgites are thought to be the residua left after extraction of MORB-type basalt, from which high-Al chromitite [49.2 < Cr# = 100 × Cr/(Cr + Al) < 53.5] crystallised with a higher proportion of ¹⁸⁷Os/¹⁸⁸Os (average of 0.1361). However, depleted harzburgites are assumed to be the residua left after extraction of hydrous boninitic melt produced by second stage partial melting of already depleted mantle due to a subducting slab, from which high-Cr chromitites (64.2 < Cr# < 85.9) with lower and heterogeneous ¹⁸⁷Os/¹⁸⁸Os ratio (average of 0.1324) were crystallised as a result of melt–rock interaction in a supra-subduction environment. Dunites around the chromite deposits are considered to be the product of melt–peridotite interaction. Most of the chromitites contain high-Cr chromite and display enrichment in IPGE (Os, Ir, Ru) over PPGE (Rh, Pt, Pd), with PGE concentrations between 61 and 1,305 ppb. Consistently, laurite-erlichmanite series minerals with various Os concentrations are found to be the most abundant PGM inclusions in chromite. Os–Ir–Ru alloy, irarsite, and kashinite, as well as Pt–Fe alloy and Pt-oxide, which are not common in ophiolitic chromitites, were also detected as magmatic PGM inclusions. Pentlandite, millerite, and, rarely heazlewoodite form the magmatic inclusions of base-metal sulphide. The presence of olivine and clinopyroxene, as well as hydrous silicate inclusions such as amphibole and phlogopite, in high-Cr chromitite supports the idea that high-Cr chromitites were formed in a supra-subduction environment.     

Factors affecting clarity of freshwater lakes in Brandenburg, Germany

In the German State Brandenburg, water clarity and the concentrations of the water quality components chlorophyll a, seston and gelbstoff were measured in 27 lakes. Correlation analysis showed, that spectral beam attenuation at 662 and 514 nm was mainly dependent on changes in chlorophyll a concentrations. In the UV-channel at 360 nm, beam attenuation depended mostly on gelbstoff.

Multiple linear regression provided a direct model of beam attenuation at 514 nm with the inputs of inorganic seston, chlorophyll a and gelbstoff. The specific beam attenuation coefficients were comparable to other natural waters around the world. An inverse model is presented, from which gelbstoff and chlorophyll a could be predicted with some accuracy from the inputs of beam attenuation coefficients at 514 and 360 nm. However, it became obvious that biological variability put major constraints on the predictive capacity of both the direct and the inverse model.

Furthermore, we observed a good correspondence of Secchi depth and the inverse of beam attenuation at 514 nm. The predictions of Secchi depth and chlorophyll a concentration from the inverse model were assessed in perspective of using this instrument instead of laborious chemical analysis for future trophic status classification according to LAWA (Länderarbeitsgemeinschaft Wasser). Predictions of trophic status were principally good when using calibrated models, however, quality of classification critically depended on predictions of chlorophyll a.     

Elimination of Interferences in the Determination of Palladium,Platinum and Rhodium Mass Fractions in Moss Samples using ICP‐MS/MS

Moss samples (Pleurozium schreberi) exposed to traffic‐related emission of Pd, Pt and Rh were analysed in this study. Successful elimination of interferences was achieved in the determination of Pd, Pt and Rh mass fractions in these samples using inductively coupled plasma‐tandem mass spectrometry (ICP‐MS/MS). Based on the results, a reliable determination of Pd, Pt and Rh mass fractions in microwave‐digested moss samples was obtained using ammonia (10% NH₃ in He) in the collision/reaction cell when ¹⁰³Rh was measured either on‐mass (103→103) or with mass‐shift (103→171) and mass‐shifts for ¹⁰⁸Pd (108→159) and ¹⁹⁵Pt (195→229) were used. The ICP‐MS/MS procedure was validated using BCR‐723 (road dust) as a reference material. In addition, a good agreement between the ICP‐MS/MS results and the results obtained with cloud point extraction and quadrupole ICP‐MS was observed for the moss samples.     

Geochemistry of polymetamorphic ultramafics (Major,Trace, Noble and Rare Earth Elements): An example from the Helvetic basement,Central Alps,Switzerland

Summary Polymetamorphic ultramafic rocks in orogenic terranes rarely preserve relic structures or minerals from their former mantle stages. The determination of their protoliths and their tectonic evolution by chemical discrimination methods is often difficult due to possible metasomatic processes. Ultramafics of the pre-Variscan Helvetic basement (Central Alps, Switzerland) have been investigated geochemically to address these problems. These ultramafics are partially to completely serpentinised. According to field observations several ultramafic lenses were part of an ophiolite suite, but distinct cumulate ultramafic lenses were also recognized. CIPW norms indicate that large parts of the ultramafics are harzburgites, but metasomatic CaO depletion may have produced an overestimation of the importance of the harzburgite protoliths. Major element distributions suggest a depleted mantle protolith. Close to chondritic or slightly depleted REE patterns are characteristics of the studied samples. The REE normalized patterns confirm the presence of harzburgites, lherzolites und cumulates. In some samples light REE enrichment processes have occurred. The noble metal concentrations are both affected (Pt-Pd-Au) und unaffected (Ir-Os-Ru) by melt infiltration processes. They suggest the presence of undepleted or slightly enriched harzburgites und more differentiated, probably cumulate ultramafics. Information obtained by different chemical elements leads to contrasting results. REE and noble metals show enrichment inconsistent with the major element depletion. Refertilization of depleted ultramafics is proposed.

---

Geochemie von polymetamorphen Ultramafiten (Haupt-, Spuren-Elemente, Edelmetalle und Seltene Erden): Ein Beispiel vom Helvetischen Grundgebirge (Zentralalpen, Schweiz)

Zusarnmenfassung Ultramafische Gesteine aus polymetamorphen orogenetischen Terrains enthalten selten Strukturen und Mineralien als Relikte aus ihren Mantelstadien. Bestimmung ihrer Protolithe und deren tektonischen Entwicklung durch geochemische Parameter wird durch metasomatische Prozesse erschwert. Ultramafite aus dem prävariszischen Sockel der Schweizer Zentralalpen wurden geochemisch untersucht, um die Aussagekraft dieser Parameter zu bestimmen. Die untersuchten Gesteine sind teilweise bis völlig serpentinisiert. Aufgrund der Felduntersuchungen wurden die Ultramafite als Teile einer ophiolithischen Suite klassifiziert, aber ultramafische Kumulate anderer Entstehungsgeschichte konnten unterschieden wurden. CIPW-Norm Berechnungen zeigen, daß Harzburgite den größten Anteil der Proben ausmachen, aber metasomatische Abreicherung an Caokönnte die Bedeutung der Harzburgite als Protolithe überbewerten. Haupt- und Spurenelemente weisen auf einen abgereicherten Mantel als Ausgangsgesteinhin. Fast chondritische bzw. leicht abgereicherte Seltene Erden verteilungsmuster sind charakteristisch. Sic belegen auch die harzburgitische, lherzolithische bzw. kumulative Natur der untersuchten Gesteine. Die Edelmetallkonzentrationen sind teilweise primär (Ir, Os, Ru) sowie beeinflußt durch Schmelzinfiltrationen (Pr, Pd und Au). Die Verteilungsmuster der Edelmetalle bezeugen die Natur des abgereicherten Mantels sowie die Gegenwart von höher differenzierten—vermutlich kumulativen—Gesteinen. Die Hinweise aus den geochemischen Untersuchungen führen zu konsistenten Ergebnissen. Die Anreicherung der Seltenen Erden und Edelmetalle ist mit der verarmten Signatur der Hauptelemente nicht vereinbar, daher wird eine sekundäre Elementanreicherung durch Schmelzinfiltration der Ultramafite vorgeschlagen.

     

Platinum-Group Element and Rhenium Concentrations in Low Abundance Reference Materials

One or two gram aliquots of twelve reference materials with low platinum-group element (PGE) abundances (Ir concentrations ranging from 30 to 510 pg g^-1) were analysed by isotope dilution ICP-MS using an on-line chromatographic matrix separation after acid digestion in a high pressure asher (HPA-S) to determine the concentrations of Ru, Pd, Re, Ir and Pt. Osmium concentrations were determined via ID-ICP-MS but as volatile OsO₄, whereas Rh concentrations were calculated by comparing the peak areas of the chromatographic peak with that of a standard solution. Validation of the method was performed and the concepts of traceability and measurement uncertainty were applied to assure comparability. The reference materials BCR-2, BHVO-1, BHVO-2, BIR-1, DNC-1, EN026 10D-3, MAG-1, RGM-1, SCo-1, SDO-1, TDB-1 and W-2 were investigated to test for their usefulness for certification. The use of TDB-1 is highly recommended because it is homogeneous at the two gram level and many values based on several different analytical procedures have been published. It is recommended that our efforts should focus on the certification of this reference material to reduce the uncertainties of its currently certified values (Pd and Pt only) and to assign certified values to the other PGE and Re. It is necessary to have at least one well-characterised RM for validation of methods applied to the analysis of PGE and Re in low abundance samples, although the matrix of TDB-1 might not completely match those of many samples.