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.     

Late-Stage Mafic Injection and Thermal Rejuvenation of the Vinalhaven Granite, Coastal Maine

The Vinalhaven intrusive complex consists mainly of coarse-grainedgranite, inward-dipping gabbro–diorite sheets, and a fine-grainedgranite core. Small bodies of porphyry occur throughout thecoarse-grained granite. The largest porphyry body (roughly 0·5km by 2·5 km) occurs with coeval gabbro, hybrid rocks,and minor fine-grained granite in the Vinal Cove complex, whichformed during the waning stages of solidification of the coarse-grainedVinalhaven granite. Porphyry contacts with surrounding coarse-grainedgranite are irregular and gradational. Compositions of wholerocks and minerals in the porphyry and the coarse-grained graniteare nearly identical. Neighboring phenocrysts in the porphyryvary greatly in degree of corrosion and reaction, indicatingthat the porphyry was well stirred. Thermal rejuvenation ofa silicic crystal mush by a basaltic influx can explain thecomposition and texture of the porphyry. Comparable rejuvenationevents have been recognized in recent studies of erupted rocks.Weakly corroded biotite phenocrysts in the porphyry requirethat hydrous interstitial melt existed in the granite duringremelting. Field relations, along with thermal calculations,suggest that cooling and crystallization of coeval mafic magmacould have generated the porphyry by thermal rejuvenation ofgranite crystal-mush containing about 20% melt. Field relationsalso suggest that some of the porphyry matrix may representnew felsic magma that was emplaced during remelting. KEY WORDS: granite; magma chamber; mafic replenishment; rejuvenation     

Thermal history of the unsaturated zone at Yucca Mountain,Nevada, USA

Secondary calcite, silica and minor amounts of fluorite deposited in fractures and cavities record the chemistry, temperatures, and timing of past fluid movement in the unsaturated zone at Yucca Mountain, Nevada, the proposed site of a high-level radioactive waste repository. The distribution and geochemistry of these deposits are consistent with low-temperature precipitation from meteoric waters that infiltrated at the surface and percolated down through the unsaturated zone. However, the discovery of fluid inclusions in calcite with homogenization temperatures (T_h) up to ∼80 °C was construed by some scientists as strong evidence for hydrothermal deposition. This paper reports the results of investigations to test the hypothesis of hydrothermal deposition and to determine the temperature and timing of secondary mineral deposition. Mineral precipitation temperatures in the unsaturated zone are estimated from calcite- and fluorite-hosted fluid inclusions and calcite δ¹⁸O values, and depositional timing is constrained by the ²⁰⁷Pb/²³⁵U ages of chalcedony or opal in the deposits. Fluid inclusion T_h from 50 samples of calcite and four samples of fluorite range from ∼35 to ∼90 °C. Calcite δ¹⁸O values range from ∼0 to ∼22‰ (SMOW) but most fall between 12 and 20‰. The highest T_h and the lowest δ¹⁸O values are found in the older calcite. Calcite T_h and δ¹⁸O values indicate that most calcite precipitated from water with δ¹⁸O values between −13 and −7‰, similar to modern meteoric waters.     

Ordovician eclogites from the Chinese Beishan: implications for the tectonic evolution of the southern Altaids

Numerous lenses of eclogite occur in a belt of augen orthogneisses in the Gubaoquan area in the southern Beishan orogen, an eastern extension of the Tianshan orogen. With detailed petrological data and phase relations, modelled in the system NCFMASHTO with thermocalc , a quantitative P–T path was estimated and defined a clockwise P–T path that showed a near isothermal decompression from eclogite facies (>15.5 kbar, 700–800 °C, omphacite + garnet) to high‐pressure granulite facies (12–14 kbar, 700–750 °C, clinopyroxene + sodic plagioclase symplectitic intergrowths around omphacite), low‐pressure granulite facies (8–9.5 kbar, ～700 °C, orthopyroxene + clinopyroxene + plagioclase symplectites and coronas surrounding garnet) and amphibolite facies (5–7 kbar, 600–700 °C, hornblende + plagioclase symplectites). The major and trace elements and Sm–Nd isotopic data suggest that most of the Beishan eclogite samples had a protolith of oceanic crust with geochemical characteristics of an enriched or normal mid‐ocean ridge basalt. The U–Pb dating of the Beishan eclogites indicates an Ordovician age of c. 467 Ma for the eclogite facies metamorphism. An ³⁹Ar/⁴⁰Ar age of c. 430 Ma for biotite from the augen gneiss corresponds to the time of retrograde metamorphism. The combined data from geological setting, bulk composition, clockwise P–T path and geochronology support a model in which the Beishan eclogites started as oceanic crust in the Palaeoasian Ocean, which was subducted to eclogite depths in the Ordovician and exhumed in the Silurian. The eclogite‐bearing gneiss belt marks the position of a high‐pressure Ordovician suture zone, and the calculated clockwise P–T path defines the progression from subduction to exhumation.     

Eclogite and carpholite-bearing metasedimentary rocks in the North Qilian suture zone, NW China: implications for Early Palaeozoic cold oceanic subduction and water transport into mantle

Low‐temperature eclogite and eclogite facies metapelite together with serpentinite and marble occur as blocks within foliated blueschist that was originated from greywacke matrix; they formed a high‐pressure low‐temperature (HPLT) subduction complex (mélange) in the North Qilian oceanic‐type suture zone, NW China. Phengite–eclogite (type I) and epidote–eclogite (type II) were recognized on the basis of mineral assemblage. Relic lawsonite and lawsonite pseudomorphs occur as inclusions in garnet from both types of eclogite. Garnet–omphacite–phengite geothermobarometry yields metamorphic conditions of 460–510 °C and 2.20–2.60 GPa for weakly deformed eclogite, and 475–500 °C and 1.75–1.95 GPa for strongly foliated eclogite. Eclogite facies metasediments include garnet–omphacite–phengite–glaucophane schist and various chloritoid‐bearing schists. Mg‐carpholite was identified in some high‐Mg chloritoid schists. P–T estimates yield 2.60–2.15 GPa and 495–540 °C for Grt–Omp–Phn–Gln schist, and 2.45–2.50 GPa and 525–530 °C for the Mg‐carpholite schist. Mineral assemblages and P–T estimates, together with isotopic ages, suggest that the oceanic lithosphere as well as pelagic to semi‐pelagic sediments have been subducted to the mantle depths (≥75 km) before 460 Ma. Blueschist facies retrogression occurred at c. 454–446 Ma and led to eclogite deformation and dehydration of lawsonite during exhumation. The peak P–Tconditions for eclogite and metapelite in the North Qilian suture zone demonstrate the existence of cold subduction‐zone gradients (6–7 °C km^?1), and this cold subduction brought a large amount of H₂O to the deep mantle in the Early Palaeozoic times.     

Discovery of Ordovician–Silurian metamorphic monazite in garnet metapelites of the Alpine External Aiguilles Rouges Massif

The pre-Mesozoic, mainly Variscan metamorphic basement of the Col de Bérard area (Aiguilles Rouges Massif, External domain) consists of paragneisses and micaschists together with various orthogneisses and metabasites. Monazite in metapelites was analysed by the electron microprobe (EMPA-CHIME) age dating method. The monazites in garnet micaschists are dominantly of Variscan age (330–300 Ma). Garnet in these rocks displays well developed growth zonations in Fe–Mg–Ca–Mn and crystallized at maximal temperatures of 670°C/7 kbar to the west and 600°C/7–8 kbar to the east. In consequence the monazite is interpreted to date a slightly pressure-dominated Variscan amphibolite-facies evolution. In mylonitic garnet gneisses, large metamorphic monazite grains of Ordovician–Silurian (~440 Ma) age but also small monazite grains of Variscan (~300 Ma) age were discovered. Garnets in the mylonitic garnet gneisses display high-temperature homogenized Mg-rich profiles in their cores and crystallized near to ~800°C/6 kbar. The Ordovician–Silurian-age monazites can be assigned to a pre-Variscan high-temperature event recorded by the homogenised garnets. These monazite age data confirm Ordovician–Silurian and Devonian–Carboniferous metamorphic cycles which were already reported from other Alpine domains and further regions in the internal Variscides.     

Determination of Gold in Twenty Geochemical Reference Samples by Flameless Atomic Absorption Spectrometry

After acid digestion, gold is extracted with MIBK and determinated by flameless atomic absorption spectrometry. The results for six USGS reference samples and fourteen French geochemical standards are presented and discussed. The agreement with working values for these standards is in the range of pm 5%.     

Differential subduction and exhumation of crustal slices in the Sulu HP-UHP metamorphic terrane: insights from mineral inclusions, trace elements, U-Pb and Lu-Hf isotope analyses of zircon in orthogneiss

Based on new evidence the Sulu orogen is divided from south‐east to north‐west into high‐pressure (HP) crustal slice I and ultrahigh‐pressure (UHP) crustal slices II and III. A combined set of mineral inclusions, cathodoluminescence images, U‐Pb SHRIMP dating and in situ trace element and Lu‐Hf isotope analyses was obtained on zircon from orthogneisses of the different slices. Zircon grains typically have three distinct domains that formed during crystallization of the magmatic protolith, HP or UHP metamorphism and late‐amphibolite facies retrogression, respectively: (i) oscillatory zoned cores, with low‐pressure (LP) mineral inclusions and Th/U > 0.38; (ii) high‐luminescent mantles (Th/U < 0.10), with HP mineral inclusions of Qtz + Grt + Arg + Phe + Ap for slice I zircon and Coe + Grt + Phe + Kfs + Ap for both slices II and III zircon; (iii) low‐luminescent rims, with LP mineral inclusions and Th/U < 0.08. Zircon U‐Pb SHRIMP analyses of inherited cores point to protolith ages of 785–770 Ma in all seven orthogneisses. The ages recorded for UHP metamorphism and subsequent retrogression in slice II zircon (c. 228 and c. 215 Ma, respectively) are significantly older than those of slice III zircon (c. 218 and c. 202 Ma, respectively), while slice I zircon recorded even older ages for HP metamorphism and subsequent retrogression (c. 245 and c. 231 Ma, respectively). Moreover, Ar‐Ar biotite ages from six paragneisses, interpreted as dating amphibolite facies retrogression, gradually decrease from HP slice I (c. 232 Ma) to UHP slice II (c. 215 Ma) and UHP slice III (c. 203 Ma). The combined data set suggests decreasing ages for HP or UHP metamorphism and late retrogression in the Sulu orogen from south‐east to north‐west. Thus, the HP‐UHP units are interpreted to represent three crustal slices, which underwent different subduction and exhumation histories. Slice I was detached from the continental lithosphere at ～55–65 km depth and subsequently exhumed while subduction of the underlying slice II continued to ～100–120 km depth (UHP) before detachment and exhumation. Slice III experienced a similar geodynamic evolution as slice II, however, both UHP metamorphism and subsequent exhumation took place c. 10 Myr later. Magmatic zircon cores from two types of orthogneiss in UHP slices II and III show similar mid‐Neoproterozoic crystallization ages, but have contrasting Hf isotope compositions (εHf_(～785) = ?2.7 to +2.2 and ?17.3 to ?11.1, respectively), suggesting their formation from distinct crustal units (Mesoproterozoic and Paleoproterozoic to Archean, respectively) during the breakup of Rodinia. The UHP and the retrograde zircon domains are characterized by lower Th/U and ¹⁷⁶Lu/¹⁷⁷Hf but higher ¹⁷⁶Hf/¹⁷⁷Hf(t) than the Neoproterozoic igneous cores. The similarity between UHP and retrograde domains indicates that late retrogression did not significantly modify chemical and isotopic composition of the UHP metamorphic system.     

Diffusion and sorption experiments using a DKS permeameter

The analysis of contaminant transport through clay liner is a relevant aspect in the design of industrial, urban and mining waste disposal systems, since these areas must be designed and operated to prevent contaminating substances from reaching underground water systems in unacceptable concentrations. The design requires an estimate of the potential contaminant transport rate. However, before any attempt at quantification can be made, values for transport mechanism control parameters must be established. Clayey materials are frequently used as contaminant barriers. In these materials, which have low hydraulic conductivity, the main contaminant transport mechanism is molecular diffusion. Parameters controlling transport for these conditions are the diffusion coefficient and sorption parameters. These parameters depend on soil constituents and characteristics as well as on the chemical constitution of the contaminant. The great complexity of the factors involved makes it necessary to determine the parameters of each type of soil. This paper discusses an equipment called DKS permeameter (diffusion, convection, sorption), for the study of soil-contaminant transport mechanisms, designed at the Institute for Soil Mechanics of the Ruhr-University Bochum, and some results obtained from its use at COPPE/Federal University of Rio de Janeiro (UFRJ), Brazil. This equipment determines the effective diffusion coefficient and sorption parameter with a better reflection of field conditions. The soil under study is a mix of sodium–bentonite that has low hydraulic conductivity (k=10⁻⁹ cm/s) with adequate liner characteristics. The result indicated the relevance of determining sorption parameters for structured soils, since the sorption perceived from batch test results using pulverised soil represents maximum soil capacity. Designs based on this parameter would overestimate the attenuation capacity of the liner.     

New data on distribution of REEs in sulfide minerals and Sm-Nd dating of ore genesis of layered basic intrusions

This paper presents data on the distribution of REEs in sulfide minerals from ore-bearing gabbronorites in the Penikat layered intrusion and the results of their isotopic-geochronological Sm-Nd study. A new procedure for determination of REEs in the samples without preliminary separating and concentrating was tested on standard samples to be further used for analysis of sulfide minerals. Analysis of the spectra of the REE distribution in sulfides represents a distribution trend that is similar to the already studied bulk rock and allows deducing that the character of the REE distribution in sulfide minerals from gabbronorites in the Penikat layered intrusion was inherited from the parent magma melt; while the formation of sulfides took place at the stage of rock crystallization. The performed complex studies allow considering that sulfides can be successfully used together with the rock-forming minerals in Sm-Nd dating of ore-bearing mafite-ultramafite intrusions.