Radiation defects in feldspars

Various radiation defects were characterized and analyzed by electron paramagnetic resonance (EPR) in 15 feldspars of different compositions after X-ray irradiation. A hole center on oxygen adjacent to two aluminum ions is formed in most feldspars, except those with very high An content. Since the hole is not localized at room temperature, clusters of more than two Al must be present in all feldspars in amounts of at least 100 ppm. Less frequent radiation defects are trivalent titanium and holes on oxygen ions adjacent to a small divalent ion of a yet unidentified nature on a T site with Si and in some cases also Pb as further neighbors. The directions of the magnetic axes for these centers allowed their assignment to specific sites in the feldspar structure. Characteristic absorption and thermolu-minescence emission bands could also be assigned to these centers. Their properties are remarkably independent of composition and Al, Si disorder of the feldspars.     

Investigation of the Matrix Effect of Mg, Si, Ca, Sc, Fe, Y, La and Lu in Pyroxene Composition Synthetic Silicate Glasses by Ion Microprobe

The dependence of the count rate of singly charged secondary ions of the elements Mg, Si, Ca, Sc, Fe, Y, La and Lu on the bulk composition of the sample (known as the matrix effect) was systematically investigated for synthetic silicate glasses using a Cameca IMS 3f ion microprobe. Matrix elements in these samples, with the composition of a Mg-Fe-Ca pyroxene, comprised Mg, Si, Ca and Fe to which were added the minor elements Sc, Y, La and Lu (each at 0.1 atom %). The matrix dependence of all elements was determined quantitatively by ratioing their count rate response to the Ca or Fe yields of the sample. Measurements were conducted using four energy offsets: 0 eV, 40 eV, 80 eV and 120 eV (each 20 eV) with primary beam currents of between 0.5 and 3 nA. For the four minor elements investigated, a non-linear dependence of the absolute sensitivity factors on the Fe content was found at all the energy ranges studied. This matrix effect decreased with increasing secondary ion energy. For the major elements Mg, Si, Ca and Fe, linear as well as non-linear dependences of the absolute sensitivity factors on the Fe content were found, depending on the element and the energy level considered. Because of their importance in the geosciences, relative sensitivity factors of the elements under study relative to Si as reference element (in some cases also relative to Mg) were determined. For low energy ions, a Fe-dependent matrix effect also occurred. For Mg, Y, La and Lu, the matrix effect vanished for some values of the secondary ions energy range.     

Preservation of organic matter and alteration of its carbon and nitrogen isotope composition during simulated and in situ early sedimentary diagenesis

The carbon and nitrogen isotope composition of organic matter has been widely used to trace biogeochemical processes in marine and lacustrine environments. In order to reconstruct past environmental changes from sedimentary organic matter, it is crucial to consider potential alteration of the primary isotopic signal by bacterial degradation in the water column and during early diagenesis in the sediments.In a series of oxic and anoxic incubation experiments, we examined the fate of organic matter and the alteration of its carbon and nitrogen isotopic composition during microbial degradation. The decomposition rates determined with a double-exponential decay model show that the more reactive fraction of organic matter degrades at similar rates under oxic and anoxic conditions. However, under oxic conditions the proportion of organic matter resistent to degradation is much lower than under anoxic conditions. Within three months of incubation the δ¹³C of bulk organic matter decreased by 1.6‰ with respect to the initial value. The depletion can be attributed to the selective preservation of ¹³C-depleted organic compounds. During anoxic decay, the δ¹⁵N values continuously decreased to about 3‰ below the initial value. The decrease probably results from bacterial growth adding ¹⁵N-depleted biomass to the residual material. In the oxic experiment, δ¹⁵N values increased by more then 3‰ before decreasing to a value indistinguishable from the initial isotopic composition. The dissimilarity between oxic and anoxic conditions may be attributed to differences in the type, timing and degree of microbial activity and preferential degradation. In agreement with the anoxic incubation experiments, sediments from eutrophic Lake Lugano are, on average, depleted in ¹³C (−1.5‰) and ¹⁵N (−1.2‰) with respect to sinking particulate organic matter collected during a long-term sediment trap study.     

EPR of V4+ and Fe3+ in titanites

EPR investigations of yellow-green titanites from four localities showed presence of V⁴⁺ and Fe³⁺. They were investigated at X-band and room temperature. For V⁴⁺ the principal values of the g matrix and ⁵¹V hyperfine splitting and the directions of their principal axes indicate presence of a VO²⁺ ion substituting for Ti. Due to a high zero-field splitting only approximate values of the fine structure parameters of Fe³⁺ could be determined. With directions of their principal axes very similar to those of V⁴⁺ this ion must also substitute for Ti. Unusually large linewidths for both ions with little variation for samples from different localities are ascribed to the reported domain structure of titanites and accumulation of impurities in the domain boundaries. While for Fe³⁺ a small variation of the fine structure parameters explains this broadening, for V⁴⁺ a distribution of g-factors equal to its total anisotropy must be responsible whereas the V=0 bond length is remarkably constant. Due to preferential incorporation of impurities in the grain boundaries a contribution of dipolar broadening cannot be excluded.     

Local relaxations around Fe3+ and Cr3+ in Al sites in minerals

Second-order zero-field splitting (ZFS) parameters from the literature for Fe³⁺ in twelve and for Cr³⁺ in seven minerals substituting for Al were evaluated by application of the superposition model. For Fe³⁺ in monoclinic site symmetries a fair agreement of the observed splitting patterns with those calculated from the crystal structure data was observed in most cases, but the distortions for Fe³⁺ appear to be usually larger than those of the unrelaxed Al sites. In cases of not too large local relaxation the unknown sign of the axialZFS parameterb ₀ ² could be predicted, in two cases a different sign than that reported was postulated. In cordierite and scolecite the reportedEPR spectra could thus be assigned to the sites with larger average bond distances. For Fe³⁺ in beryl the relaxation of the axial site can be deduced within narrow limits. For Cr³⁺ significantly larger differences between observed and calculatedZFS patterns are found suggesting additional relaxations due to the non-spherical electron distribution in the ground state of this ion.