Lippmann Diagrams: Theory and Application to Carbonate Systems

Since 1980 when F. Lippmann's seminal paper appeared, ourunderstanding of solubility equilibria involving ionic solidsolutions has been advanced by theoretical considerations as wellas careful experimental studies designed to determine excess Gibbsfunctions. A unified theory of solid-solution aqueous-solutionequilibria as well as the thermodynamic background of thephenomenon of ``stoichiometric saturation' are reviewed.It is shown that Lippmann diagrams effectively summarize thethermodynamic basis of solid-solute aqueous-solution equilibria ofsparingly soluble metal carbonate systems. Clearly, the predictivepower of these diagrams may be limited due to kineticrestrictions. Only when dissolution and precipitation areessentially reversible, favourable conditions to synthesizehomogeneous solid phases can be derived from studies of equilibria.     

Zircon M127 – A Homogeneous Reference Material for SIMS U–Pb Geochronology Combined with Hafnium,Oxygen and,Potentially, Lithium Isotope Analysis

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS‐determined mean U–Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for ²⁰⁶Pb/²³⁸U and 0.67676 ± 0.00023 for ²⁰⁷Pb/²³⁵U (weighted means, 2s uncertainties). Its ²⁰⁶Pb/²³⁸U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The δ¹⁸O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio (determined by solution ICP‐MS) is 0.282396 ± 0.000004 (2s). The SIMS‐determined δ⁷Li value is ?0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 μg g^?1 Li (2s). Zircon M127 contains ~ 923 μg g^?1 U. The moderate degree of radiation damage corresponds well with the time‐integrated self‐irradiation dose of 1.82 × 10¹⁸ alpha events per gram. This observation, and the (U–Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U–Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.     

Exploring the impact of diagenesis on (isotope) geochemical and microstructural alteration features in biogenic aragonite

For the Quaternary and Neogene, aragonitic biogenic and abiogenic carbonates are frequently exploited as archives of their environment. Conversely, pre‐Neogene aragonite is often diagenetically altered and calcite archives are studied instead. Nevertheless, the exact sequence of diagenetic processes and products is difficult to disclose from naturally altered material. Here, experiments were performed to understand biogenic aragonite alteration processes and products. Shell subsamples of the bivalve Arctica islandica were exposed to hydrothermal alteration. Thermal boundary conditions were set at 100°C, 175°C and 200°C. These comparably high temperatures were chosen to shorten experimental durations. Subsamples were exposed to different ¹⁸O‐depleted fluids for durations between two and twenty weeks. Alteration was documented using X‐ray diffraction, cathodoluminescence, fluorescence and scanning electron microscopy, as well as conventional and clumped isotope analyses. Experiments performed at 100°C show redistribution and darkening of organic matter, but lack evidence for diagenetic alteration, except in Δ₄₇ which show the effects of annealing processes. At 175°C, valves undergo significant aragonite to calcite transformation and neomorphism. The δ¹⁸O signature supports transformation via dissolution and reprecipitation, but isotopic exchange is limited by fluid migration through the subsamples. Individual growth increments in these subsamples exhibit bright orange luminescence. At 200°C, valves are fully transformed to calcite and exhibit purple‐blue luminescence with orange bands. The δ¹⁸O and Δ₄₇ signatures reveal exchange with the aqueous fluid, whereas δ¹³C remains unaltered in all experiments, indicating a carbonate‐buffered system. Clumped isotope temperatures in high‐temperature experiments show compositions in broad agreement with the measured temperature. Experimentally induced alteration patterns are comparable with individual features present in Pleistocene shells. This study represents a significant step towards sequential analysis of diagenetic features in biogenic aragonites and sheds light on reaction times and threshold limits. The limitations of a study restricted to a single test organism are acknowledged and call for refined follow‐up experiments.     

Archaean high-K granitoids produced by remelting of earlier Tonalite–Trondhjemite–Granodiorite (TTG) in the Sangmelima region of the Ntem complex of the Congo craton,southern Cameroon

We present a geochemical and isotopic study that, consistent with observed field relations, suggest Sangmelima late Archaean high-K granite was derived by partial melting of older Archaean TTG. The TTG formations are sodic-trondhjemitic, showing calcic and calc-alkalic trends and are metaluminous to peraluminous. High-K granites in contrast show a potassic calc-alkaline affinity that spans the calcic, calc-alkalic, alkali-calcic and alkalic compositions. The two rock groups (TTG and high-K granites) on the other hand are both ferroan and magnesian. They have a similar degree of fractionation for LREE but a different one for HREE. Nd model ages and Sr/Y ratios define Mesoarchaean and slab-mantle derived magma compositions respectively, with Nb and Ti anomalies indicating a subduction setting for the TTG. Major and trace element in addition to Sr and Nd isotopic compositions support field observations that indicate the derivation of the high-K granitic group from the partial melting of the older TTG equivalent at depth. Geochemical characteristics of the high-K granitic group are therefore inherited features from the TTG protolith and cannot be used for determining their tectonic setting. The heat budget required for TTG partial melting is ascribed to the upwelling of the mantle marked by a doleritic event of identical age as the generated high-K granite melts. The cause of this upwelling is related to linear delamination along mega-shear zones in an intracontinental setting.     

Phanerozoic tectonothermal history of the Arabian–Nubian shield in the Eastern Desert of Egypt: evidence from fission track and paleostress data

To constrain the post-Pan-African evolution of the Arabian–Nubian Shield, macro-scale tectonic studies, paleostress and fission track data were performed in the Eastern Desert of Egypt. The results provide insights into the processes driving late stage vertical motion and the timing of exhumation of a large shield area. Results of apatite, zircon and sphene fission track analyses from the Neoproterozoic basement indicate two major episodes of exhumation. Sphene and zircon fission track data range from 339 to 410 Ma and from 315 to 366 Ma, respectively. The data are interpreted to represent an intraplate thermotectonic episode during the Late Devonian–Early Carboniferous. At that time, the intraplate stresses responsible for deformation, uplift and erosion, were induced by the collision of Gondwana with Laurussia which started in Late Devonian times. Apatite fission track data indicate that the second cooling phase started in Oligocene and was related to extension, flank uplift and erosion along the actual margin of the Red Sea. Structural data collected from Neoproterozoic basement, Late Cretaceous and Tertiary sedimentary cover suggest two stages of rift formation. (1) Cretaceous strike-slip tectonics with sub-horizontal σ1 (ENE/WSW) and σ3 (NNW/SSE), and sub-vertical σ2 resulted in formation of small pull-apart basins. Basin axes are parallel to the trend of Pan-African structural elements which acted as stress guides. (2) During Oligocene to Miocene the stress field changed towards horizontal NE–SW extension (σ3), and sub-vertical σ1. Relations between structures, depositional ages of sediments and apatite fission track data indicate that the initiation of rift flank uplift, erosion and plate deformation occurred nearly simultaneously.     

Zircon U–Pb ages and O–Nd isotopic composition of basement rocks in the North Qinling Terrain, central China: evidence for provenance and evolution

The Qinling Group was previously interpreted as the oldest Precambrian basement unit of the North Qinling Terrain, recording its formation and early crustal evolution. The Qinling Group consists predominantly of gneisses, amphibolites, and marbles, which underwent multi-phase deformation and metamorphism. In order to better constrain the provenance and tectonic setting of this group and the evolution of the North Qinling orogenic belt, in situ U–Pb dating and oxygen isotopic analysis of zircons in combination with whole-rock geochemistry and Sr–Nd isotope analysis was performed on the two dominant rock types, amphibolite and felsic gneiss. Felsic gneisses exhibit enrichment of LREEs and LILEs (Rb, Ba, Th, K, Pb), negative Eu anomalies and depletion of HFSEs (Nb, Ta, P, Ti). The rocks have slightly elevated δ¹⁸O values (6.5–9.3 ‰) and initial ε _Nd values of ?4.6 corresponding to two-stage Nd model age of 1.99 Ga. Amphibolites are also enriched in LILEs and LREEs and depleted in Nb and Ta and have homogeneous δ¹⁸O values (5.0–6.0 ‰), but higher initial ε _Nd values (2.8–3.3) and younger two-stage Nd model ages (1.29–1.24 Ga) compared to the gneisses. The zircon age record indicates that the gneisses and amphibolites were formed in a ~960 Ma volcanic arc environment rather than in a rift setting as previously suggested. A major metamorphic event took place during the Early Paleozoic. Based on the age spectrum of detrital zircons, the Qinling Group is interpreted as an autonomous geological unit, which was mainly derived mostly from 1,000 to 900 Ma old granitoid rocks. The North Qinling Terrain can be regarded as a remnant of the Grenville orogenic belt with an early Neoproterozoic evolution different from that of the North and South China blocks.     

Zircon age and Nd–Hf isotopic composition of the Yunnan Tethyan belt,southwestern China

The Baoshan block of the Tethyan Yunnan, southwestern China, is considered as northern part of the Sibumasu microcontinent. Basement of this block that comprises presumably greenschist-facies Neoproterozoic metamorphic rocks is covered by Paleozoic to Mesozoic low-grade metamorphic sedimentary rocks. This study presents zircon ages and Nd–Hf isotopic composition of granites generated from crustal reworking to reveal geochemical feature of the underlying basement. Dating results obtained using the single zircon U–Pb isotopic dilution method show that granites exposed in the study area formed in early Paleozoic (about 470 Ma; Pingdajie granite) and in late Yanshanian (about 78–61 Ma, Late Cretaceous to Early Tertiary; Huataolin granite). The early Paleozoic granite contains Archean to Mesoproterozoic inherited zircons and the late Yanshanian granite contains late Proterozoic to early Paleozoic zircon cores. Both granites have similar geochemical and Nd–Hf isotopic charateristics, indicating similar magma sources. They have whole-rock T _DM(Nd) values of around 2,000 Ma and zircon T _DM(Hf) values clustering around 1,900–1,800 and 1,600–1,400 Ma. The Nd–Hf isotopic data imply Paleoproterozoic to Mesoproterozoic crustal material as the major components of the underlying basement, being consistent with a derivation from Archean and Paleoproterozoic terrains of India or NW Australia. Both granites formed in two different tectonic events similarly originated from intra-crustal reworking. Temporally, the late Yanshanian magmatism is probably related to the closure of the Neotethys ocean. The early Paleozoic magmatism traced in the Baoshan block indicates a comparable history of the basements during early Paleozoic between the SE Asia and the western Tethyan belt, such as the basement outcrops in the Alpine belt and probably in the European Variscides that are considered as continental blocks drifting from Gondwana prior to or simultaneously with those of the SE Asia.     

Further Information of the Associated Li Deposits in the No.6 Coal Seam at Jungar Coalfield,Inner Mongolia,Northern China

Total 138 coal samples and 14 parting samples were taken from the No. 6 Seam of the Jungar Coalfield, Inner Mongolia. These samples were analysed by optical microscopy, sequential chemical extraction procedure (SCEP), inductively coupled plasma mass spectrometry (ICP-MS), X-ray powder diffraction (XRD), and scanning electron microscope in conjunction with an energy-dispersive X-ray spectrometer (SEM-EDX) analysis. The results indicate that the Li contents have reached the industrial grade of the coal associated Li deposit, and the total Li reserves have reached 2406600 tons, that is, 5157000 tons Li2O in the No. 6 seam in the Jungar Coalfield. The sequential chemical extraction procedure results suggest that the Li concentration is mainly related to inorganic matter. The minerals in the coals consist of kaolinite, boehmite, chlorite-group mineral, quartz, calcite, pyrite, siderite and amorphous clay material. Some Li could be absorbed by clay minerals in the Li-bearing coal seam. The chlorite phase?could be?most likely the host for a part of Li. The Yinshan Oldland should be the most possible source of Li of the coal.     

Holocene climate evolution of the Ugii Nuur basin,Mongolia

In order to evaluate the Holocene palaeoenvironmental evolution of the Ugii Nuur basin, central Mongolia, investigations on chemical and mineralogical properties of lacustrine sediments were carried out on a 630 cm sediment core from lake Ugii Nuur. The interpretation of the record is based on a principal component analysis （PCA） of the elemental composition of the samples. The results show that lacustrine deposition started at 10.6 kyr BP. Low lake level conditions were identified during the Early Holocene （10.6-7.9 kyr BP）. The Mid Holocene （7.9-4.2 kyr BP） was characterized by generally higher lake levels and thus higher moisture supply, but it experienced strong climatic fluctuations. Arid conditions prevailed from 4.2-2.8 kyr BP and were followed by a stable, more humid phase until today.