Dorrit E. Jacob

MPI‐DING reference glasses for in situ microanalysis: New reference values for element concentrations and isotope ratios

We present new analytical data of major and trace elements for the geological MPI-DING glasses KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, BM90/21-G, T1-G, and ATHO-G. Different analytical methods were used to obtain a large spectrum of major and trace element data, in particular, EPMA, SIMS, LA-ICPMS, and isotope dilution by TIMS and ICPMS. Altogether, more than 60 qualified geochemical laboratories worldwide contributed to the analyses, allowing us to present new reference and information values and their uncertainties (at 95% confidence level) for up to 74 elements. We complied with the recommendations for the certification of geological reference materials by the International Association of Geoanalysts (IAG). The reference values were derived from the results of 16 independent techniques, including definitive (isotope dilution) and comparative bulk (e.g., INAA, ICPMS, SSMS) and microanalytical (e.g., LA-ICPMS, SIMS, EPMA) methods. Agreement between two or more independent methods and the use of definitive methods provided traceability to the fullest extent possible. We also present new and recently published data for the isotopic compositions of H, B, Li, O, Ca, Sr, Nd, Hf, and Pb. The results were mainly obtained by high-precision bulk techniques, such as TIMS and MC-ICPMS. In addition, LA-ICPMS and SIMS isotope data of B, Li, and Pb are presented.

Diamondiferous eclogites from Siberia: Remnants of Archean oceanic crust

We have investigated eight diamond-bearing bimineralic eclogite xenoliths from the Udachnaya Mine, Yakutia, Siberia, in terms of major elements, 87Sr86Sr−, 143Nd144Nd and oxygen isotopic ratios. The β18O-values, measured with the new laser-fluorination technique, are different from mantle values and range between 5.19 and 7.38%. with an average error of 0.08%.. Strontium and neodymium initial isotopic ratios for cpx are between 0.70226 and 0.70699 and 0.51170 and 0.51257, respectively. Chemically and petrographically, the Siberian eclogites are very similar to the South African eclogite suite from Roberts Victor or Bellsbank, the most important similarities being the late Archean age (2.76 Ga) and the δ18O values that deviate from mantle values. However, differences exist in detail, as no samples with δ18O values lower than mantle values have yet been reported from Siberia and the cesium concentrations of the Siberian eclogites are generally lower than those of the Roberts Victor eclogite suite. The data obtained from the studied sample suite are best explained by a model proposing an origin from Archean oceanic crust that was intensely altered prior to subduction to mantle depths. Using oxygen isotopic values, the effects of seawater alteration can be shown and the composition of the unaltered protolith qualitatively estimated. We propose that mantle eclogites from kimberlites were generated by a globally operating subduction process during the late Archean and that differences between samples from different cratons are small compared to their similarities.

Evolution of the Archaean crust by delamination and shallow subduction

The Archaean oceanic crust was probably thicker than present-day oceanic crust owing to higher heat flow and thus higher degrees of melting at mid-ocean ridges. These conditions would also have led to a different bulk composition of oceanic crust in the early Archaean, that would probably have consisted of magnesium-rich picrite (with variably differentiated portions made up of basalt, gabbro, ultramafic cumulates and picrite). It is unclear whether these differences would have influenced crustal subduction and recycling processes, as experiments that have investigated the metamorphic reactions that take place during subduction have to date considered only modern mid-ocean-ridge basalts. Here we present data from high-pressure experiments that show that metamorphism of ultramafic cumulates and picrites produces pyroxenites, which we infer would have delaminated and melted to produce basaltic rocks, rather than continental crust as has previously been thought. Instead, the formation of continental crust requires subduction and melting of garnet-amphibolite—formed only in the upper regions of oceanic crust—which is thought to have first occurred on a large scale during subduction in the late Archaean. We deduce from this that shallow subduction and recycling of oceanic crust took place in the early Archaean, and that this would have resulted in strong depletion of only a thin layer of the uppermost mantle. The misfit between geochemical depletion models and geophysical models for mantle convection (which include deep subduction) might therefore be explained by continuous deepening of this depleted layer through geological time.

Evidence for Archean ocean crust with low high field strength element signature from diamondiferous eclogite xenoliths

Abstract Late Archean (2.57 Ga) diamond-bearing eclogite xenoliths from Udachnaya, Siberia, exhibit geochemical characteristics including variation in oxygen isotope values, and correlations of δ 18 O with major elements and radiogenic isotopes which can be explained by an origin as subducted oceanic crust. Trace element analyses of constituent garnet and clinopyroxene by Laser-ICPMS are used to reconstruct whole-rock trace element compositions, which indicate that the eclogites have very low high field strength element (HFSE) concentrations and Zr/Hf and Nb/Ta ratios most similar to modern island arcs or ultradepleted mantle. Although hydrothermal alteration on the Archean sea floor had enough geochemical effect to allow the recognition of its effects in the eclogites and thus diagnose them as former oceanic crust, it was not severe enough to erase many other geochemical features of the original igneous rocks, particularly the relatively immobile HFSEs. Correlations of the trace element patterns with oxygen isotopes show that some, generally Mg-richer, eclogites originated as lavas, whereas others have lower δ 18 O and higher Sr and Eu contents indicating an origin as plagioclase-bearing intrusive rocks formed in magma chambers within the ocean crust. Major and trace element correlations demonstrate that the eclogites are residues after partial melting during the subduction process, and that their present compositions were enriched in MgO by this process. The original lava compositions were picritic, but not komatiitic, whereas the intrusives had lower, basaltic MgO contents. The HFSE signature of the eclogites may indicate that ocean floor basalts of the time were relatively close to island arcs and recycled material, which would be consistent with a larger number of smaller oceanic plates. Their composition appears to indicate that komatiitic ocean crust compositions were restricted to the early Archean which is not known to be represented among the eclogite xenolith population.

Trace element geochemistry of coesite-bearing eclogites from the Roberts Victor kimberlite, Kaapvaal craton

Trace element characteristics of seven coesite-bearing eclogitic xenoliths from the Roberts Victor kimberlite demonstrate that this suite of eclogites originated as gabbroic cumulates in oceanic crust that was subsequently subducted. All but one of the garnets show positive Eu anomalies, accompanied by a flat heavy rare earth pattern, which is atypical of garnet, but characteristic of plagioclase, arguing for a considerable amount of plagioclase in the protoliths. Forward modelling of the accumulation of liquidus minerals from primitive komatiitic, picritic, and basaltic liquids suggests that at least some of the eclogite protoliths were not derived from basaltic parental liquids, whereas derivation from either komatiitic or picritic liquids is possible. The reconstructed eclogite bulk rocks compare favourably with oceanic gabbros from ODP hole 735B (SW Indian Ridge), even to the extent that oxygen isotopic systematics show signs of low-temperature seawater alteration. However, the oxygen isotope trends are the reverse of what is expected for cumulates in the lower section of the oceanic crust. These new findings show that δ18O values in eclogitic xenoliths, despite being sound indicators for their interaction with hydrothermal fluids at low pressure, do not necessarily bear a simple relationship with the inferred oceanic crustal stratigraphy of the protoliths.

Amorphous calcium carbonate in the shells of adult Unionoida

Shells of adult individuals from two different bivalve families, Hyriopsis cumingii and Diplodon chilensis patagonicus, were studied by Micro-Raman spectroscopy and Focussed Ion Beam-assisted TEM. The shells contain amorphous calcium carbonate in a zone at the interface between the periostracum and the prismatic layer. In this area, the initial prism structures protrude from the inner periostracum layer and it is demonstrated that these structures systematically consist of highly disordered and amorphous calcium carbonate. Within this zone, ordered and disordered areas are intermingled discounting the existence of a crystallization front and favouring models of domainal crystallization processes via so-called mesocrystals. These observations are the first documentation of the use of amorphous calcium carbonate as a precursor phase by adult mollusc species and lend further support to hypotheses postulating widespread use of amorphous phases as building material of skeletal tissue in biology.

Structural characterization and chemical composition of aragonite and vaterite in freshwater cultured pearls

Abstract Vaterite and aragonite polymorphs in freshwater cultured pearls from mussels of the genus Hyriopsis (Unionidae) were structurally and compositionally characterized by Raman spectroscopy, Micro computer tomography, high resolution field emission scanning electron microscopy, electron microprobe analysis and laser ablation inductively coupled plasma mass spectrometry. The appearance of vaterite in pearls is related to the initial stages of biomineralization, although we demonstrate that vaterite can not be a precursor to aragonite. It is not related to a particular crystal habit and therefore does not have a structural functionality in the pearls. Larger contents of elements typically bound to organic molecules, such as P and S in vaterite, as well as larger total organic contents in vaterite as opposed to aragonite in conjunction with larger concentrations of Mn2+ and Mg2+, imply a stabilizing role of organic macromolecules and X2+ ions for biological vaterite. Distribution coefficients between aragonite and vaterite for provenance-independent elements, such as Mn and Mg (0.27 and 0.04, respectively) agree very well with those observed in fish otoliths.

The compositional variability of eudialyte-group minerals

Abstract Eudialyte-group minerals (EGM) represent the most important index minerals of persodic agpaitic systems. Results are presented here of a combined EPMA, Mössbauer spectroscopy and LA-ICP-MS study and EGM which crystallized in various fractionation stages from different parental melts and mineral assemblages in silica over- and undersaturated systems are compared. Compositional variability is closely related to texture, allowing for reconstruction of locally acting magmatic to hydrothermal processes. Early-magmatic EGM are invariably dominated by Fe whereas hydrothermal EGM can be virtually Fe-free and form pure Mn end-members. Hence the Mn/Fe ratio is the most suitable fractionation indicator, although crystal chemistry effects and co-crystallizing phases play a secondary role in the incorporation of Fe and Mn into EGM. Mössbauer spectroscopy of EGM from three selected occurrences indicates the Fe3+/∑Fe ratio to be governed by the hydration state of EGM rather than by the oxygen fugacity of the coexisting melt. Negative Eu anomalies are restricted to EGM that crystallized from alkali basaltic parental melts while EGM from nephelinitic parental melts invariably lack negative Eu anomalies. Even after extensive differentiation intervals, EGM reflect properties of their respective parental melts and the fractionation of plagioclase and other minerals such as Fe-Ti oxides, amphibole and sulphides.

Novel findings in patients with primary hyperoxaluria type III and implications for advanced molecular testing strategies

Identification of mutations in the HOGA1 gene as the cause of autosomal recessive primary hyperoxaluria (PH) type III has revitalized research in the field of PH and related stone disease. In contrast to the well-characterized entities of PH type I and type II, the pathophysiology and prevalence of type III is largely unknown. In this study, we analyzed a large cohort of subjects previously tested negative for type I/II by complete HOGA1 sequencing. Seven distinct mutations, among them four novel, were found in 15 patients. In patients of non-consanguineous European descent the previously reported c.700+5G>T splice-site mutation was predominant and represents a potential founder mutation, while in consanguineous families private homozygous mutations were identified throughout the gene. Furthermore, we identified a family where a homozygous mutation in HOGA1 (p.P190L) segregated in two siblings with an additional AGXT mutation (p.D201E). The two girls exhibiting triallelic inheritance presented a more severe phenotype than their only mildly affected p.P190L homozygous father. In silico analysis of five mutations reveals that HOGA1 deficiency is causing type III, yet reduced HOGA1 expression or aberrant subcellular protein targeting is unlikely to be the responsible pathomechanism. Our results strongly suggest HOGA1 as a major cause of PH, indicate a greater genetic heterogeneity of hyperoxaluria, and point to a favorable outcome of type III in the context of PH despite incomplete or absent biochemical remission. Multiallelic inheritance could have implications for genetic testing strategies and might represent an unrecognized mechanism for phenotype variability in PH.

Bio-vaterite formation by glycoproteins from freshwater pearls

A 48 kDa acidic and putative calcium-binding glycoprotein was isolated from pearls of the freshwater mussel Hyriopsis cumingii. This protein was compared with a related 46 kDa polypeptide, obtained from the nacreous shell of the same species. Separation by two-dimensional gel electrophoresis revealed that the difference in molecular weight is due to the higher extent of glycosylation of the 48 kDa protein existing in pearls. Evidence is presented that the sugar moieties of the protein contribute to crystal growth, starting with the nucleation step. In in vitro precipitation experiments, the 48 kDa glycoprotein of pearls directed the formation of round-shaped vaterite crystals while the 46 kDa glycoprotein of shells promoted formation of small irregular calcite particles. Furthermore, both proteins, 48 kDa/46 kDa, comprised carbonic anhydrase activity that has been implicated in CaCO(3) formation. Thus, a function of the isolated glycoproteins in biomineralization is proposed together with the mechanism by which they can stabilize different calcium carbonate polymorphs.