Composition of barian mica in multiphase solid inclusions from orogenic garnet peridotites as evidence of mantle metasomatism in a subduction zone setting

Multiphase solid inclusions in minerals formed at ultra-high-pressure (UHP) provide evidence for the presence of fluids during deep subduction. This study focuses on barian mica, which is a common phase in multiphase solid inclusions enclosed in garnet from mantle-derived UHP garnet peridotites in the Saxothuringian basement of the northern Bohemian Massif. The documented compositional variability and substitution trends provide constraints on crystallization medium of the barian mica and allow making inferences on its source. Barian mica in the multiphase solid inclusions belongs to trioctahedral micas and represents a solid solution of phlogopite KMg₃(Si₃Al)O₁₀(OH)₂, kinoshitalite BaMg₃(Al₂Si₂)O₁₀(OH)₂ and ferrokinoshitalite BaFe₃(Al₂Si₂)O₁₀(OH)₂. In addition to Ba (0.24–0.67 apfu), mica is significantly enriched in Mg (X_Mg ~ 0.85 to 0.95), Cr (0.03–0.43 apfu) and Cl (0.04–0.34 apfu). The substitution vector involving Ba in the I-site which describes the observed chemical variability can be expressed as BaFe^IVAlClK_?1Mg_?1Si_?1(OH)_?1. A minor amount of Cr and ^VIAl enters octahedral sites following a substitution vector ^VI(Cr,Al)₂□^VI(Mg,Fe)_?3 towards chromphyllite and muscovite. As demonstrated by variable Ba and Cl contents positively correlating with Fe, barian mica composition is partly controlled by its crystal structure. Textural evidence shows that barian mica, together with other minerals in multiphase solid inclusions, crystallized from fluids trapped during garnet growth. The unusual chemical composition of mica reflects the mixing of two distinct sources: (1) an internal source, i.e. the host peridotite and its garnet, providing Mg, Fe, Al, Cr, and (2) an external source, represented by crustal-derived subduction-zone fluids supplying Ba, K and Cl. At UHP–UHT conditions recorded by the associated diamond-bearing metasediments (c. 1100 °C and 4.5 GPa) located above the second critical point in the pelitic system, the produced subduction-zone fluids transporting the elements into the overlying mantle wedge had a solute-rich composition with properties of a hydrous melt. The occurrence of barian mica with a specific chemistry in barium-poor mantle rocks demonstrates the importance of its thorough chemical characterization.     

Olivine in ultramafic lamprophyres: chemistry,crystallisation, and melt sources of Siberian Pre- and post-trap aillikites

We studied olivines from the Devonian pre-trap (the Ilbokich occurrence) and the Triassic post-trap (the Chadobets occurrence) carbonate-rich ultramafic lamprophyres (UMLs) in the southwestern portion of the Siberian craton. On the basis of detailed investigations of major, minor, and trace-element distributions, we have reconstructed the main processes that control the origins of these olivines. These include fractional crystallisation from melt, assimilation, and fractional crystallisation processes with orthopyroxene assimilation, melt-reaction diffusive re-equilibration, alkali enrichment, and CO₂ degassing of the melt. Furthermore, we inferred the composition of the sources of the primary UML melt and their possible correlations with proto-kimberlitic melts, as well as the influence of the Triassic Siberian plume on the composition of the lithospheric mantle. The main differences between olivines from the Ilbokich and the Chadobets aillikites were that the olivines from the former had more magnesium-rich cores (Mg# = 89.2?±?0.2), had Mg- and Cr-rich transition zones (Mg# = 89.7?±?0.2 and 300–500 ppm Cr), had lower Ni (up to 3100 ppm) and Li (1.4–1.5 ppm), and had higher B (0.8–2.6 ppm) contents, all at higher Fo values (90–86), relative to the olivines from the latter (Mg# = 88–75; 200–300 ppm Cr; up to 3400 ppm Ni; 1.4–2.4 ppm Li; 0.4–2.2 ppm B). The Siberian aillikite sources contained a significant amount of metasomatic material. Phlogopite-rich MARID-type veins provided the likely metasomatic component in the pre-trap Devonian Ilbokich aillikite source, whereas the Triassic Chadobets aillikitic post-trap melts were derived from a source with a significant carbonate component. A comparison of UML olivines with olivines from the pre-trap and post-trap Siberian kimberlites shows a striking similarity. This suggests that the carbonate component in the aillikitic source could have been produced by evolved kimberlite melts. The differences in the lithospheric metasomatic component that contributed to pre-trap and post-trap aillikitic melts can be interpreted as reflections of the thermal impact of the Siberian Traps, which reduced phlogopite-bearing metasomes within the southwestern Siberian sub-continental lithospheric mantle.     

Synthesis of monticellite–forsterite and merwinite–forsterite symplectites in the CaO–MgO–SiO<Subscript>2</Subscript> model system: influence of temperature and water content on microstructure evolution

Homogeneous single crystals of synthetic monticellite with the composition \({\text{Ca}}_{0.88}{\text{Mg}}_{1.12}{\text{SiO}}_4\) (Mtc I) were annealed in a piston-cylinder apparatus at temperatures between 1000 and \(1200\,^{\circ }\hbox {C}\), pressures of 1.0–1.4 GPa, for run durations from 10 min to 24 h and applying bulk water contents ranging from 0.0 to 0.5 wt% of the total charge. At these conditions, Mtc I breaks down to a fine-grained, symplectic intergrowth. Thereby, two types of symplectites are produced: a first symplectite type (Sy I) is represented by an aggregate of rod-shaped forsterite immersed in a matrix of monticellite with end-member composition (Mtc II), and a second symplectite type (Sy II) takes the form of a lamellar merwinite–forsterite intergrowth. Both symplectites may form simultaneously, where the formation of Sy I is favoured by the presence of water. Sy I is metastable with respect to Sy II and is successively replaced by the latter. For both symplectite types, the characteristic spacing of the symplectite phases is independent of run duration and is only weeakly influenced by the water content, but it is strongly temperature dependent. It varies from about 400 nm at \(1000\,^{\circ }\hbox {C}\) to 1200 nm at \(1100\,^{\circ }\hbox {C}\) in Sy I, and from 300 nm at \(1000\,^{\circ }\hbox {C}\) to 700 nm at \(1200\,^{\circ }\hbox {C}\) in Sy II. A thermodynamic analysis reveals that the temperature dependence of the characteristic spacing of the symplectite phases is due to a relatively high activation energy for chemical segregation by diffusion within the reaction front as compared to the activation energy for interface reactions at the reaction front. The temperature dependence of the characteristic lamellar spacing and the temperature-time dependence of overall reaction progress have potential for applications in geo-thermometry and geo-speedometry.     

Magma evolution beneath Bequia,Lesser Antilles,deduced from petrology of lavas and plutonic xenoliths

Extrusive and intrusive igneous rocks represent different parts of a magmatic system and ultimately provide complementary information about the processes operating beneath volcanoes. To shed light on such processes, we have examined and quantified the textures and mineral compositions of plutonic and cumulate xenoliths and lavas from Bequia, Lesser Antilles arc. Both suites contain assemblages of iddingsitized olivine, plagioclase, clinopyroxene and spinel with rare orthopyroxene and ilmenite. Mineral zoning is widespread, but more protracted in lavas than xenoliths. Plagioclase cores and olivine have high anorthite (An?≤?98) and low forsterite (Fo?≤?84) compositions respectively, implying crystallisation from a hydrous mafic melt that was already fractionated. Xenolith textures range from adcumulate to orthocumulate with variable mineral crystallisation sequences. Textural criteria are used to organize the xenoliths into six groups. Amphibole, notably absent from lavas, is a common feature of xenoliths, together with minor biotite and apatite. Bulk compositions of xenoliths deviate from the liquid line of descent of lavas supporting a cumulate origin with varying degrees of reactive infiltration by evolved hydrous melts, preserved as melt inclusions in xenolith crystals. Volatile saturation pressures in melt inclusions indicate cumulate crystallization over a 162–571 MPa pressure range under conditions of high dissolved water contents (up to 7.8 wt% H₂O), consistent with a variety of other thermobarometric estimates. Phase assemblages of xenoliths are consistent with published experimental data on volatile-saturated low-magnesium and high-alumina basalts and basaltic andesite from the Lesser Antilles at pressures of 200–1000 MPa, temperatures of 950–1050 °C and dissolved H₂O contents of 4–7 wt%. Once extracted from mid-crustal mushes, residual melts ascend to higher levels and undergo H₂O-saturated crystallization in shallow, pre-eruptive reservoirs to form phenocrysts and glomerocrysts. The absence of amphibole from lavas reflects instability at low pressures, whereas its abundance in xenoliths testifies to its importance in mid-crustal differentiation processes. A complex, vertically extensive (6 to at least 21 km depth) magmatic system is inferred beneath Bequia. Xenoliths represent fragments of the mush incorporated into ascending magmas. The widespread occurrence of evolved melts in the mush, but the absence of erupted evolved magmas, in contrast to islands in the northern Lesser Antilles, may reflect the relative immaturity of the Bequia magmatic system.     

Phase-equilibrium geobarometers for silicic rocks based on rhyolite-MELTS. Part 4: Plagioclase,orthopyroxene, clinopyroxene,glass geobarometer,and application to Mt. Ruapehu,New Zealand

A new phase equilibria geobarometer determines magmatic storage and crystallization conditions, including pressure, temperature, oxygen fugacity (\({f_{{{\text{o}}_2}}}\)), and the presence of a fluid phase for glass-bearing rocks containing the assemblage plagioclase?+?pyroxene(s). This newly developed geobarometer can better constrain crystallization conditions of shallow (<?500 MPa; <~?20 km), glass-bearing andesites to dacites. The geobarometer utilizes rhyolite-MELTS to determine crystallization conditions in natural pumice and scoria samples. The validity of the geobarometer is tested by comparing it to results from experiments. Uncertainties are assessed using Monte Carlo simulations. We apply the geobarometer to the plag?+?opx?+?cpx-bearing system of Mt. Ruapehu, in the southern Taupo Volcanic Zone, New Zealand. The samples from Mt. Ruapehu are tested from ~?5 to ~?400 MPa and from super-liquidus to 90% crystalline (~ 1200 to ~ 700 °C). Mt. Ruapehu serves as a methodological testing ground for the geobarometer, and results from our geobarometer agree with recent Mt. Ruapehu studies. Results show a distribution of crystallization pressures ranging from 50 to 150 MPa (~?2.0 to 5.9 km) for different eruptions, with modes of 110 MPa (~ 4.3 km) and 130 MPa (~ 5.1 km). These are consistent with field interpretations of different eruptive styles based on juvenile clast textures and previous knowledge of the magma plumbing system. Mt. Ruapehu magmas are fluid saturated, with \({f_{{{\text{o}}_2}}}\) of ΔQFM ~ + 1 (NNO).     

Zoning and exsolution in alkali feldspars from Laacher See volcano (Western Germany): constraints on temperature history prior to eruption

Compositional zoning and exsolution patterns of alkali feldspars in carbonatite-bearing cognate syenites from the 6.3 km³ (D.R.E) phonolitic Laacher See Tephra (LST) deposit in western Germany (12.9 ka) are reported. These rocks represent the cooler outer portion and crystal-rich products of a cooling magma reservoir at upper crustal levels. Major and trace-element difference between cores and rims in sanidine crystals represent two generations of crystal growth separated by unmixing of a carbonate melt. Trace-element differences measured by LA–ICP–MS are in accordance with silicate–carbonate unmixing. Across the core–rim boundary, we extracted gray-scale profiles from multiple accumulations of back-scattered electron images. Gray scales directly represent K/Na ratios owing to low concentrations of Ba and Sr (<?30 ppm). Diffusion gradients are modeled to solve for temperature using known pre-eruptive U–Th zircon ages (0–20 ky) of each sample (Schmitt et al., J Petrol 51:1053–1085, 2010). Estimated temperatures range from 630 °C to 670 °C. For the exsolution boundaries, a diffusive homogenization model is constrained by the solvus temperature of ~ 712^_725 °C and gives short time scales of only 15–50 days. Based on our results, we present a model for the temperature–time history of these rocks. The model also constrains the thermal variation across the cooling crystal-rich carapace of the magma reservoir over 20 ka and suggests a thermal reactivation of cumulates, the cooling carapace, and probably the entire system only a few years prior to the explosive eruption of the remaining molten core of the phonolitic magma reservoir.     

The accuracy of standard enthalpies and entropies for phases of petrological interest derived from density-functional calculations

The internal energies and entropies of 21 well-known minerals were calculated using the density functional theory (DFT), viz. kyanite, sillimanite, andalusite, albite, microcline, forsterite, fayalite, diopside, jadeite, hedenbergite, pyrope, grossular, talc, pyrophyllite, phlogopite, annite, muscovite, brucite, portlandite, tremolite, and CaTiO₃–perovskite. These thermodynamic quantities were then transformed into standard enthalpies of formation from the elements and standard entropies enabling a direct comparison with tabulated values. The deviations from reference enthalpy and entropy values are in the order of several kJ/mol and several J/mol/K, respectively, from which the former is more relevant. In the case of phase transitions, the DFT-computed thermodynamic data of involved phases turned out to be accurate and using them in phase diagram calculations yields reasonable results. This is shown for the Al₂SiO₅ polymorphs. The DFT-based phase boundaries are comparable to those derived from internally consistent thermodynamic data sets. They even suggest an improvement, because they agree with petrological observations concerning the coexistence of kyanite?+?quartz?+?corundum in high-grade metamorphic rocks, which are not reproduced correctly using internally consistent data sets. The DFT-derived thermodynamic data are also accurate enough for computing the P–T positions of reactions that are characterized by relatively large reaction enthalpies (>?100 kJ/mol), i.e., dehydration reactions. For reactions with small reaction enthalpies (a few kJ/mol), the DFT errors are too large. They, however, are still far better than enthalpy and entropy values obtained from estimation methods.     

The Neogene and Quaternary of England: landscape evolution,tectonics, climate change and their expression in the geological record

During the Neogene and Quaternary, tectonic and climatic processes have had a profound impact upon landscape evolution in England and, perhaps as far back as 0.9 Ma, patterns of early human occupation. Until the Late Miocene, large-scale plate tectonic processes were the principal drivers of landscape evolution causing localised basin inversion and widespread exhumation. This drove, in places, the erosion of several kilometres of Mesozoic cover rocks and the development of a regional unconformity across England and the North Sea Basin. By the Pliocene, the relative influence of tectonics on landscape evolution waned as the background tectonic stress regime evolved and climatic influences became more prominent. Global-scale climate-forcing increased step-wise during the Plio-Pleistocene amplifying erosional and depositional processes that operated within the landscape. These processes caused differential unloading (uplift) and loading (subsidence) of the crust (‘denudational isostasy’) in areas undergoing net erosion (upland areas and slopes) and deposition (basins). Denudational isostasy amplified during the Mid-Pleistocene Transition (c.0.9 Ma) as landscapes become progressively synchronised to large-scale 100 ka ‘eccentricity’ climate forcing. Over the past 0.5 Ma, this has led to the establishment of a robust climate record of individual glacial/interglacial cycles enabling comparison to other regional and global records. During the Last Glacial-Interglacial Transition and early Holocene (c.16–7 ka), evidence for more abrupt (millennial/centennial) scale climatic events has been discovered. This indicates that superimposed upon the longer-term pattern of landscape evolution is a more dynamic response of the landscape to local and regional drivers.     

The stratigraphical signature of the Anthropocene in England and its wider context

The Anthropocene deposits of England, here regarded as those formed after ～1950 CE, are now extensive, take various forms, and may be characterized and recognized by a number of stratigraphic signals, such as artificial radionuclides, pesticide residues, microplastics, enhanced fly ash levels, concrete fragments and a novel variety of ‘technofossils’ and neobiotic species. They include the uppermost parts of both ‘natural’ deposits such as the sediment layers formed in lakes and estuaries, and more directly human-made or human-influenced ones such as landfill deposits and the ‘artificial ground’ beneath urban areas and around major constructions. ‘Negative deposits’ include the worked areas of quarries and regions such as the English Fenland, where thick peat deposits have ablated to leave a strongly modified underlying landscape, and extend beneath into the subterranean realm as mine workings, metro systems and boreholes. The production of these is still rapidly increasing and evolving in character, while the early signs of global change, such as warming, sea level rise, and modifications to biotic assemblages, are beginning to further modify the emerging geology of this new phase of Earth history.