Petrogenesis of rift-related tephrites, phonolites and trachytes (Central European Volcanic Province, Rhon, FRG): Constraints from Sr, Nd, Pb and O isotopes

The volcanic rocks of the Rhön area (Central European Volcanic Province, Germany) belong to a moderately alkali basaltic suite that is associated with minor tephriphonolites, phonotephrites, tephrites, phonolites and trachytes. Based on isotope sytematics (87Sr/86Sr: 0.7033–0.7042; 143Nd/144Nd: 0.51279–0.51287; 206Pb/204Pb: 19.1–19.5), the inferred parental magmas formed by variable degrees of partial melting of a common asthenospheric mantle source (EAR: European Asthenospheric Reservoir of Cebriá and Wilson, 1995). Tephrites, tephriphonolites, phonotephrites, phonolites and trachytes show depletions and enrichments in some trace elements (Sr, Ba, Nb, Zr, Y) indicating that they were generated by broadly similar differentiation processes that were dominated by fractionation of olivine, clinopyroxene, amphibole, apatite and titaniferous magnetite ± plagioclase ± alkalifeldspar. The fractionated samples seem to have evolved by two distinct processes. One is characterized by pure fractional crystallization indicated by increasing Nb (and other incompatible trace element) concentrations at virtually constant 143Nd/144Nd ~ 0.51280 and 87Sr/86Sr ~ 0.7035. The other process involved an assimilation–fractional crystallization (AFC) process where moderate assimilation to crystallization rates produced evolved magmas characterized by higher Nb concentrations at slightly lower 143Nd/144Nd down to 0.51275. Literature data for some of the evolved rocks show more variable 87Sr/86Sr ranging from 0.7037 to 0.7089 at constant 143Nd/144Nd ~ 0.51280. These features may result from assimilation of upper crustal rocks by highly differentiated low-Sr (< 100 ppm Sr) lavas. However, based on the displacement of the differentiated rocks from this study towards lower 143Nd/144Nd ratios and modeled AFC processes in 143Nd/144Nd vs. 87Sr/86Sr and 207Pb/204Pb vs. 143Nd/144Nd space assimilation of lower crustal rocks seems more likely. The view that assimilation of lower crustal rocks played a role is confirmed by high-precision double-spike Pb isotope data that reveal higher 207Pb/204Pb ratios (15.62–15.63) in the differentiated rocks than in the primitive basanites (15.58–15.61). This is compatible with incorporation of radiogenic Pb from lower crustal xenoliths (207Pb/204Pb: 15.63–15.69) into the melt. However, 206Pb/204Pb ratios are similar for the differentiated rocks (19.13–19.35) and the primitive basanites (19.12–19.55) implying that assimilation involved an ancient crustal end member with a higher U/Pb ratio than the mantle source of the basanites. In addition, alteration-corrected δ18O values of the differentiated rocks range from c. 5 to 7‰ which is the same range as observed in the primitive alkaline rocks. This study confirms previous interpretations that highlighted the role of AFC processes in the evolution of alkaline volcanic rocks in the Rhön area of the Central European Volcanic Province.

Highly accurate isotope composition measurements by a miniature laser ablation mass spectrometer designed for in situ investigations on planetary surface

An experimental procedure for precise and accurate measurements of isotope abundances by a miniature laser ablation mass spectrometer for space research is described. The measurements were conducted on different untreated NIST standards and galena samples by applying pulsed UV laser radiation (266 nm, 3 ns and 20 Hz) for ablation, atomisation, and ionisation of the sample material. Mass spectra of released ions are measured by a reflectron-type time-of-flight mass analyser. A computer controlled performance optimiser was used to operate the system at maximum ion transmission and mass resolution. At optimal experimental conditions, the best relative accuracy and precision achieved for Pb isotope compositions are at the per mill level and were obtained in a range of applied laser irradiances and a defined number of accumulated spectra. A similar relative accuracy and precision was achieved in the study of Pb isotope compositions in terrestrial galena samples. The results for the galena samples are similar to those obtained with a thermal ionisation mass spectrometer (TIMS). The studies of the isotope composition of other elements yielded relative accuracy and precision at the per mill level too, with characteristic instrument parameters for each element. The relative accuracy and precision of the measurements is degrading with lower element/isotope concentration in a sample. For the elements with abundances below 100 ppm these values drop to the percent level. Depending on the isotopic abundances of Pb in minerals, 207Pb/206Pb ages with accuracy in the range of tens of millions of years can be achieved.

K-feldspar hygrochronology

The significance of the multi-isotopic record preserved in K-feldspars is assessed on samples from the Aar metagranite, Central Alps, Switzerland having very tight independent geological constraints. Stepwise leaching reveals that two diachronically grown K-feldspar generations coexist: Kfs-1 (≥ 35 Ma old, Ca-poor, Rb-Cl-rich, with low 87Sr/86Sr and high 206Pb/204Pb) and Kfs-2 (≤ 10 Ma old, antithetic isotopic signatures deriving from external fluids). Microtextures imaged by cathodoluminescence, backscattered electrons, and electron probe microanalysis are patchy and chemically heterogeneous, with pronounced enrichments in Ba in the retrogressed regions. This confirms the simultaneous presence of fluid-dominated retrogression and recrystallization and isotopic inheritance. The staircase-shaped 40Ar/39Ar age spectrum correlates with the Ca/K and Cl/K signatures. This reflects a mixture of heterochemical K-feldspar generations, and not an intracrystalline Ar gradient caused by diffusion. The shape of the age spectrum and the in vacuo release kinetics proceed from entirely different physical and geological phenomena. What K-feldspars can be effectively used for is to constrain the timing of the fluids that interacted with them by multi-isotopic analyses, rather than to model a “cooling history” from 39Ar release alone. The identification of multiple mineral generations by imaging combined with multi-isotopic analysis enables the accurate dating of the events of a multistage evolution after the initial crystallization of the rock in which the minerals occur.

Accumulation rates and predominant atmospheric sources of natural and anthropogenic Hg and Pb on the Faroe Islands

A monolith representing 5420 14C yr of peat accumulation was collected from a blanket bog at Myrarnar, Faroe Islands. The maximum Hg concentration (498 ng/g at a depth of 4.5 cm) coincides with the maximum concentration of anthropogenic Pb (111 μg/g). Age dating of recent peat accumulation using 210Pb (CRS model) shows that the maxima in Hg and Pb concentrations occur at AD 1954 ± 2. These results, combined with the isotopic composition of Pb in that sample (206Pb/207Pb = 1.1720 ± 0.0017), suggest that coal burning was the dominant source of both elements. From the onset of peat accumulation (ca. 4286 BC) until AD 1385, the ratios Hg/Br and Hg/Se were constant (2.2 ± 0.5 × 10-4 and 8.5 ± 1.8 × 10-3, respectively). Since then, Hg/Br and Hg/Se values have increased, also reaching their maxima in AD 1954. The age date of the maximum concentrations of anthropogenic Hg and Pb in the Faroe Islands is consistent with a previous study of peat cores from Greenland and Denmark (dated using the atmospheric bomb pulse curve of 14C), which showed maximum concentrations in AD 1953. The average rate of atmospheric Hg accumulation from 1520 BC to AD 1385 was 1.27 ± 0.38 μg/m2/yr. The Br and Se concentrations and the background Hg/Br and Hg/Se ratios were used to calculate the average rate of natural Hg accumulation for the same period, 1.32 ± 0.36 μg/m2/yr and 1.34 ± 0.29 μg/m2/yr, respectively. These fluxes are similar to the preanthropogenic rates obtained using peat cores from Switzerland, southern Greenland, southern Ontario, Canada, and the northeastern United States. Episodic volcanic emissions and the continual supply of marine aerosols to the Faroe Islands, therefore, have not contributed significantly to the Hg inventory or the Hg accumulation rates, relative to these other areas. The maximum rate of Hg accumulation was 34 μg/m2/yr. The greatest fluxes of anthropogenic Hg accumulation calculated using Br and Se, respectively, were 26 and 31 μg/m2/yr. The rate of atmospheric Hg accumulation in 1998 (16 μg/m2/yr) is comparable to the values recently obtained by atmospheric transport modeling for Denmark, the Faroe Islands, and Greenland.