Insights into the complexity of crustal differentiation: K2O‐poor leucosomes within metasedimentary migmatites from the Southern Marginal Zone of the Limpopo Belt,South Africa

Differentiation of the continental crust is the result of complex interactions between a large number of processes, which govern partial melting of the deep crust, magma formation and segregation, and magma ascent to significantly higher crustal levels. The anatectic metasedimentary rocks exposed in the Southern Marginal Zone of the Limpopo Belt represent an unusually well‐exposed natural laboratory where the portion of these processes that operate in the deep crust can be directly investigated in the field. The formation of these migmatites occurred via absent incongruent melting reactions involving biotite, which produced cm‐ to m‐scale, K₂O‐poor garnet‐bearing stromatic leucosomes, with high Ca/Na ratios relative to their source rocks. Field investigation combined with geochemical analyses, and phase equilibrium modelling designed to investigate some aspects of disequilibrium partial melting show that the outcrop features and compositions of the leucosomes suggest several steps in their evolution: (1) Melting of a portion of the source, with restricted plagioclase availability due to kinetic controls, to produce a magma (melt + entrained peritectic minerals in variable proportions relative to melt); (2) Segregation of the magma at near peak metamorphic conditions into melt accumulation sites (MAS), also known as future leucosome; (3a) Re‐equilibration of the magma with a portion of the bounding mafic residuum via chemical diffusion (H₂O, K₂O), which triggers the co‐precipitation of quartz and plagioclase in the MAS; (3b) Extraction of melt‐dominated magma to higher crustal levels, leaving peritectic minerals entrained from the site of the melting reaction, and the minerals precipitated in the MASs to form the leucosome in the source. The key mechanism controlling this behaviour is the kinetically induced restriction of the amount of plagioclase available to the melting reaction. This results in elevated melt H₂O and K₂O and chemical potential gradient for these components across the leucosome/mafic residuum contact. The combination of all of these processes accurately explains the composition of the K₂O‐poor leucosomes. These findings have important implications for our understanding of melt segregation in the lower crust and minimum melt residency time which, according to the chemical modelling, is <5 years. We demonstrate that in some migmatitic granulites, the leucosomes constitute a type of felsic refractory residuum, rather than evidence of failed magma extraction. This provides a new insight into the ways that source heterogeneity may control anatexis.     

Geochemical and isotopic characterization of trace fossil infillings: New insights on tracemaker activity after the K/Pg impact event

Geochemical and isotopic analyses of the Cretaceous–Paleogene (K/Pg) boundary deposits were conducted at the Caravaca section (External Subbetic, southeast of Spain) in order to evaluate the recovery of the macrobenthic tracemaker community and the bioturbational disturbance. Samples from the infilling material of several lower Danian dark-colored trace fossils (Chondrites, Planolites, Thalassinoides and Zoophycos) located in the uppermost 8-cm of the light upper Maastrichtian strata, as well as samples from the host sedimentary rock of these trace fossils, were analyzed and compared with data from the lower Danian deposits. The values of element ratios indicative of extraterrestrial contamination (Cr/Al, Co/Al and Ni/Al) are higher in the infilling trace fossil material than in the upper Maastrichtian and lower Danian deposits, which suggests a contribution of the ejecta layer. Regarding the isotope composition, the δ¹³C values are lower in the infilling material than in the Maastrichtian host sedimentary rocks surrounding the traces, while the δ¹⁸O are higher in the infilling material. The geochemical and isotopic compositions of the infilling material evidence the unconsolidated character of the sediment, including the red boundary layer. Softground conditions confirm a relatively rapid recovery by the macrobenthic tracemaker community, starting a few millimeters above the K/Pg boundary layer. The mixture of the infilling material of the trace fossils moreover reveals a significant macrobenthic tracemaker activity affecting K–Pg boundary transition sediments that may have significantly altered original signatures.     

Field evidence for normal fault linkage and relay ramp evolution: the Kırkağaç Fault Zone,western Anatolia (Turkey)

Linking of normal faults forms at all scales as a relay ramp during growth stages and represents the most efficient way for faults to lengthen during their progressive formation. Here, I study the linking of normal faulting along the active K?rka?aç Fault Zone within the west Anatolian extensional system to reconstruct fault interaction in time and space using both field- and computer-based data. I find that (i) connecting of the relay zone/ramp occurred with two breaching faults of different generations and that (ii) the propagation was facilitated by the presence of pre-existing structures, inherited from the ?zmir-Bal?kesir transfer zone. Hence, the linkage cannot be compared directly to a simple fault growth model. Therefore, I propose a combined scenario of both hangingwall and footwall fault propagation mechanisms that explain the present-day geometry of the composite fault line. The computer-based analyses show that the approximate slip rate is 0.38 mm/year during the Quaternary, and a NE–SW-directed extension is mainly responsible for the recent faulting along the K?rka?aç Fault Zone. The proposed structural scenario also highlights the active fault termination and should be considered in future seismic hazard assessments for the region that includes densely populated settlements.     

渤海蓬莱9-1中生代花岗岩体岩石地球化学特征及其区域构造意义

蓬莱9-1花岗岩体是渤海海域首次发现的中生代花岗岩,鉴于渤海海域在华北克拉通中的重要构造位置,该花岗岩的形成时代和成因机制的研究对区域构造研究具有重大意义。锆石LA-ICP-MS U-Pb定年结果表明该花岗岩体形成于中侏罗世160~165Ma。花岗岩属于高钾钙碱性系列,为准铝质-过铝质花岗岩;富Al_2O_3(14.84%~17.19%)和Sr(485×10~(-6)~909×10~(-6)),贫Y(0.66×10~(-6)~1.39×10~(-6))和Yb(小于2.0×10~(-6)),无铕的负异常,多数样品表现为铕的弱正异常,表现出C-型埃达克岩特征。表明渤海地区在160~165Ma期间处于挤压地壳增厚环境下,以地壳减薄为标志的克拉通破坏过程彼时尚未发生,其区域动力学环境可能仍处于华北板块-华南板块碰撞拼接的影响范围内。     

Molybdenum Mass Fractions and Isotopic Compositions of International Geological Reference Materials

The double‐spike method with multi‐collector inductively coupled plasma‐mass spectrometry was used to measure the Mo mass fractions and isotopic compositions of a set of geological reference materials including the mineral molybdenite, seawater, coral, as well as igneous and sedimentary rocks. The long‐term reproducibility of the Mo isotopic measurements, based on two‐year analyses of NIST SRM 3134 reference solutions and seawater samples, was ≤ 0.07‰ (two standard deviations, 2s, n = 167) for δ^98/95Mo. Accuracy was evaluated by analyses of Atlantic seawater, which yielded a mean δ^98/95Mo of 2.03 ± 0.06‰ (2s, n = 30, relative to NIST SRM 3134 = 0‰) and mass fraction of 0.0104 ± 0.0006 μg g^?1 (2s, n = 30), which is indistinguishable from seawater samples taken world‐wide and measured in other laboratories. The comprehensive data set presented in this study serves as a reference for quality assurance and interlaboratory comparison of high‐precision Mo mass fractions and isotopic compositions.     

Copper Speciation in a Collection of Geochemical Reference Materials Using Sequential Extraction and Evaluation of the Validity Using XANES Spectroscopy

Copper speciation in a collection of Japanese geochemical reference materials (JSO‐1, JLk‐1, JSd‐1, ‐2, ‐3 and ‐4, JMs‐1 and JMs‐2) was achieved by sequential extraction and characterised using X‐ray absorption near‐edge structure spectroscopy. In the first step of the extraction, referred to as the acid fraction, between 1% and 20% total Cu within the reference materials was extracted. Such a result is typically accounted for by absorption of Cu onto clay minerals. However, the presence of Cu sulfate (an oxidation product of chalcopyrite) was observed in some of the stream sediments affected by mining activity (JSd‐2 and JSd‐3) instead. Copper was extracted in the reducible fraction (targeting Fe hydroxide and Mn oxide) (2–49% total Cu). Between 2% and 51% Cu was extracted in the oxidised fraction (targeting sulfides and organic matter). X‐ray absorption near‐edge structure spectroscopy clarified that the reducible fraction consisted of Cu bound to Fe hydroxide, whereas the oxidised fraction was a mixture of Cu bound to humic acid (HA) and Cu sulfide. In the oxidisable fraction, chalcopyrite was the predominant species identified in JSd‐2, and Cu bound to HA was the major species identified in JSO‐1 (a soil sample).     

Identification of Uranyl Minerals Using Oxygen K‐Edge X‐Ray Absorption Spectroscopy

Although most of the world's uranium exists as pitchblende or uraninite, this mineral can be weathered to a great variety of secondary uranium minerals, most containing the uranyl cation. Anthropogenic uranium compounds can also react in the environment, leading to spatial–chemical alterations that could be useful for nuclear forensics analyses. Soft X‐ray absorption spectroscopy (XAS) has the advantages of being non‐destructive, element‐specific and sensitive to electronic and physical structure. The soft X‐ray probe can also be focused to a spot size on the order of tens of nanometres, providing chemical information with high spatial resolution. However, before XAS can be applied at high spatial resolution, it is necessary to find spectroscopic signatures for a variety of uranium compounds in the soft X‐ray spectral region. To that end, we collected the near edge X‐ray absorption fine structure (NEXAFS) spectra of a variety of common uranyl‐bearing minerals, including uranyl carbonates, oxyhydroxides, phosphates and silicates. We find that uranyl compounds can be distinguished by class (carbonate, oxyhydroxide, phosphate or silicate) based on their oxygen K‐edge absorption spectra. This work establishes a database of reference spectra for future spatially resolved analyses. We proceed to show scanning X‐ray transmission microscopy (STXM) data from a schoepite particle in the presence of an unknown contaminant.     

High Precision Sr‐Nd‐Hf‐Pb Isotopic Compositions of USGS Reference Material BCR‐2

The Lamont‐Doherty Earth Observatory radiogenic isotope group has been systematically measuring Sr‐Nd‐Pb‐Hf isotopes of USGS reference material BCR‐2 (Columbia River Basalt 2), as a chemical processing and instrumental quality control monitor for isotopic measurements. BCR‐2 is now a widely used geochemical inter‐laboratory reference material (RM), with its predecessor BCR‐1 no longer available. Recognising that precise and accurate data on RMs is important for ensuring analytical quality and for comparing data between different laboratories, we present a compilation of multiple digestions and analyses made on BCR‐2 during the first author's dissertation research. The best estimates of Sr, Nd and Hf isotope ratios and measurement reproducibilities, after filtering at the 2s level for outliers, were ⁸⁷Sr/⁸⁶Sr = 0.705000 ± 11 (2s, 16 ppm, n = 21, sixteen digestions, one outlier), ¹⁴³Nd/¹⁴⁴Nd = 0.512637 ± 13 (2s, 25 ppm, n = 27, thirteen digestions, one outlier) and ¹⁷⁶Hf/¹⁷⁷Hf = 0.282866 ± 11 (2s, 39 ppm, n = 25, thirteen digestions, no outliers). Mean Nd and Hf values were within error of those reported by Weis et al. (2006, 2007) in their studies of RMs; mean Sr values were just outside the 2s uncertainty range of both laboratories. Moreover, a survey of published Sr‐Nd‐Hf data shows that our results fall within the range of reported values, but with a smaller variability. Our Pb isotope results on acid leached BCR‐2 aliquots (n = 26, twelve digestions, two outliers) were ²⁰⁶Pb/²⁰⁴Pb = 18.8029 ± 10 (2s, 55 ppm), ²⁰⁷Pb/²⁰⁴Pb = 15.6239 ± 8 (2s, 52 ppm), ²⁰⁸Pb/²⁰⁴Pb = 38.8287 ± 25 (2s, 63 ppm). We confirm that unleached BCR‐2 powder is contaminated with Pb, and that sufficient leaching prior to digestion is required to achieve accurate values for the uncontaminated Pb isotopic compositions.     

Community‐Derived Standards for LA‐ICP‐MS U‐(Th‐)Pb Geochronology – Uncertainty Propagation,Age Interpretation and Data Reporting

The LA‐ICP‐MS U‐(Th‐)Pb geochronology international community has defined new standards for the determination of U‐(Th‐)Pb ages. A new workflow defines the appropriate propagation of uncertainties for these data, identifying random and systematic components. Only data with uncertainties relating to random error should be used in weighted mean calculations of population ages; uncertainty components for systematic errors are propagated after this stage, preventing their erroneous reduction. Following this improved uncertainty propagation protocol, data can be compared at different uncertainty levels to better resolve age differences. New reference values for commonly used zircon, monazite and titanite reference materials are defined (based on ID‐TIMS) after removing corrections for common lead and the effects of excess ²³⁰Th. These values more accurately reflect the material sampled during the determination of calibration factors by LA‐ICP‐MS analysis. Recommendations are made to graphically represent data only with uncertainty ellipses at 2s and to submit or cite validation data with sample data when submitting data for publication. New data‐reporting standards are defined to help improve the peer‐review process. With these improvements, LA‐ICP‐MS U‐(Th‐)Pb data can be considered more robust, accurate, better documented and quantified, directly contributing to their improved scientific interpretation.