Geochemical variation among small eruptive centers in the central SVZ of the Andes: An evaluation of subduction, mantle and crustal influences

Subduction zone magmatism is an important and extensively studied topic in igneous geochemistry. Recent studies focus on from where arc magmas are generated, how subduction components (fluids or melts) are fluxed into the source of the magmas, and whether or how the subduction components affect partial melting processes beneath volcanic arcs at convergent boundaries. ^ At 39.5°S in the Central Southern Volcanic Zone of the Andes, Volcano Villarrica is surrounded by a suite of Small Eruptive Centers (SEC). The SECs are located mostly to the east and northeast of the stratovolcano and aligned along the Liquine-Ofqui Fault Zone, the major fracture system in this area. Former studies observed the geochemical patterns of the SECs differ distinctively from those of V. Villarrica and suggested there may be a relationship between the compositions of the volcanic units and their edifice sizes. This work is a comprehensive geochemical study on the SECs near V. Villarrica, using a variety of geochemical tracers and tools including major, trace and REE elements, Li-Be-B elements, Sr-Nd-Pb isotopes and short-lived isotopes such as U-series and 10Be. In this work, systematic differences between the elemental and isotopic compositions of the SECs and those of V. Villarrica are revealed and more importantly, modeled in terms of magmatic processes occurring at continental arc margins. Detailed modeling calculations in this work reconstruct chemical compositions of the primary magmas, source compositions, compositions and percentages of different subduction endmembers mixed into the source, degrees of partial melting and different time scales of the SECs and V. Villarrica, respectively. Geochemical characteristics and possible origins of the two special SECs—andesitic Llizan, with crustal signatures, and Rucapillan, to the northwest toward the trench, are also discussed in this work. ^

An investigation into the Hawaiian mantle from a xenolithic perspective

Salt Lake Crater (SLC), on the island of Oahu, Hawaii, is best known for its wide variety of crustal and mantle xenoliths. SLC is only the second locality in oceanic regimes where deeper portions of the upper mantle (i.e., garnet-bearing xenoliths) have been sampled. These garnet-bearing xenoliths, that contain clinopyroxene (cpx), orthopyroxene (opx), olivine, and garnet, are the focus of this study Opx is present in small amounts. Cpx has exsolved opx, spinel, and garnet. In addition, many xenoliths contain spinel-cored garnets. In some xenoliths, opx crystals contain exsolved cpx and spinel. Olivine, cpx, and garnet are in chemical equilibrium with each other. Opx is not in chemical equilibrium with the other dominant minerals. ^ The origin of these xenoliths is interpreted on the basis of liquidus phase relations in the simplified system CaO-MgO-Al2O3-SiO 2 (CMAS) system at 3.0 and 5.0 GPa. The occurrence of spinel-cored garnets and the Ol-Cpx-Gt assemblage suggests that the depth of crystallization of the SLC xenoliths examined was ∼100–110 km (i.e., uppermost asthenosphere). ^ The experimental study is concerned with the equilibrium melting of garnet clinopyroxenite at 2.0–2.5 GPa and it explores the role of such melting process in the generation of tholeiitic and alkalic lavas in ocean island basalts (OIBs). The starting material is a tholeiitic picrite in terms of its normative composition. Its solidus temperature is 1295 ± 15°C and 1332 ± 15°C at 2.0 and 2.5 GPa, respectively. At 2.0 GPa, the liquidus phase is opx that is in reaction relation with the melt. It reacts out at ∼40°C below the liquidus as cpx and spinel appear. Garnet appears long after opx disappearance. Opx is absent in runs at 2.5 GPa. Cpx and garnet appear simultaneously on the liquidus at 2.5 GPa, and are the only assemblage throughout the melting interval. At both the pressures, the partial melts are olivine-hypersthene normative at high melt fraction ( F), becoming moderately to strongly nepheline-normative, as F decreases. It is concluded that the involvement of CO 2 (and perhaps H2O) is necessary for the generation of alkalic melts in most OIBs. ^

Origin of the Grande Ronde Formation flows, Columbia River flood basalt group

Lavas belonging to the Grande Ronde Formation (GRB) constitute about 63% of the Columbia River Basalt Group (CRBG), a flood basalt province in the NW United States. A puzzling feature is the lack of phenocrysts (< 5%) in these chemically evolved lavas. Based mainly on this observation it has been hypothesized that GRB lavas were nearly primary melts generated by large-scale melting of eclogite. Another recent hypothesis holds that GRB magmas were extremely hydrous and rose rapidly from the mantle such that the dissolved water kept the magmas close to their liquidi. I present new textural and chemical evidence to show that GRB lavas were neither primary nor hydrous melts but were derived from other melts via efficient fractional crystallization and mixing in shallow intrusive systems. Texture and chemical features further suggest that the melt mixing process may have been exothermic, which forced variable melting of some of the existing phenocrysts. ^ Finally, reported here are the results of efforts to simulate the higher pressure histories of GRB using COMAGMAT and MELTS softwares. The intent was to evaluate (1) whether such melts could be derived from primary melts formed by partial melting of a peridotite source as an alternative to the eclogite model, or if bulk melting of eclogite is required; and (2) at what pressure such primary melts could have been in equilibrium with the mantle. I carried out both forward and inverse modeling. The best fit forward model indicates that most primitive parent melts related to GRB could have been multiply saturated at ∼1.5--2.0 GPa. I interpret this result to indicate that the parental melts last equilibrated with a peridotitic mantle at 1.5--2.0 GPa and such partial melts rose to ∼0.2 GPa where they underwent efficient mixing and fractionation before erupting. These models suggest that the source rock was not eclogitic but a fertile spinel lherzolite, and that the melts had ∼0.5% water. ^

Thermodynamic description and phase transformation of highly symmetrical monoatomic structures

Based on theoretical considerations an explanation for the temperature dependence of the thermal expansion and the bulk modulus is proposed. A new equation state is also derived. Additionally a physical explanation for the latent heat of fusion is presented. These theoretical predictions are tested against experiments on highly symmetrical monatomic structures. ^ The volume is not an independent variable and must be broken down into its fundamental components when the relationships to the pressure and temperature are defined. Using zero pressure and temperature reference frame, the initial parameters, volume at zero pressure and temperature[V°], bulk modulus at zero temperature [K°] and volume coefficient of thermal expansion at zero pressure[α°] are defined. ^ The new derived EoS is tested against the experiments on perovskite and epsilon iron. The Root-mean-square-deviations (RMSD) of the residuals of the molar volume, pressure, and temperature are in the range of the uncertainty of the experiments. ^ Separating the experiments into 200 K ranges, the new EoS was compared to the most widely used finite strain, interatomic potential, and empirical isothermal EoSs such as the Burch-Murnaghan, the Vinet, and the Roy-Roy respectively. Correlation coefficients, RMSD's of the residuals, and Akaike Information Criteria were used for evaluating the fitting. Based on these fitting parameters, the new p-V-T EoS is superior in every temperature range relative to the investigated conventional isothermal EoS. ^ The new EoS for epsilon iron reproduces the preliminary-reference earth-model (PREM) densities at 6100-7400 K indicating that the presence of light elements might not be necessary to explain the Earth's inner core densities. ^ It is suggested that the latent heat of fusion supplies the energy required for overcoming on the viscous drag resistance of the atoms. The calculated energies for melts formed from highly symmetrical packing arrangements correlate very well with experimentally determined latent heat values. ^ The optical investigation of carhonado-diamond is also part of the dissertation. The collected first complete infrared FTIR absorption spectra for carhonado-diamond confirm the interstellar origin for the most enigmatic diamonds known as carbonado. ^

Investigation of Mantle Dynamics from Platinum Group Elements and Rhenium-Osmium Isotope Systematics of Mantle Xenoliths from Oahu, Hawaii

Intraplate volcanism that has created the Hawaiian-Emperor seamount chain is generally thought to be formed by a deep-seated mantle plume. While the idea of a Hawaiian plume has not met with substantial opposition, whether or not the Hawaiian plume shows any geochemical signal of receiving materials from the Earth’s Outer Core and how the plume may or may not be reacting with the overriding lithosphere remain debatable issues. In an effort to understand how the Hawaiian plume works I report on the first in-situ sulfides and bulk rock Platinum Group Element (PGE) concentrations, together with Os isotope ratios on well-characterized garnet pyroxenite xenoliths from the island of Oahu in Hawaii. The sulfides are Fe-Ni Monosulfide Solid Solution and show fractionated PGE patterns. Based on the major elements, Platinum Group Elements and experimental data I interpret the Hawaiian sulfides as an immiscible melt that separated from a melt similar to the Honolulu Volcanics (HV) alkali lavas at a pressure-temperature condition of 1530 ± 100OC and 3.1±0.6 GPa., i.e. near the base or slightly below the Pacific lithosphere. The 187Os/188Os ratios of the bulk rock vary from subchondritic to suprachondritic (0.123-0.164); and the 187Os/188Os ratio strongly correlates with major element, High Field Strength Element (HFSE), Rare Earth Element (REE) and PGE abundances. These correlations strongly suggest that PGE concentrations and Os isotope ratios reflect primary mantle processes. I interpret these correlations as the result of melt-mantle reaction at the base of the lithosphere: I suggest that the parental melt that crystallized the pyroxenites selectively picked up radiogenic Os from the grain boundary sulfides, while percolating through the Pacific lithosphere. Thus the sampled pyroxenites essentially represent crystallized melts from different stages of this melt-mantle reaction process at the base of the lithosphere. I further show that the relatively low Pt/Re ratios of the Hawaiian sulfides and the bulk rock pyroxenites suggest that, upon ageing, such pyroxenites plus their sulfides cannot generate the coupled 186Os- 187Os isotope enrichments observed in Hawaiian lavas. Therefore, recycling of mantle sulfides of pyroxenitic parentage is unlikely to explain the enriched Pt-Re-Os isotope systematics of plume-derived lavas.

Arc crust-magma interaction in the Andean Southern Volcanic Zone from thermobarometry, mineral composition, radiogenic isotope and rare earth element systematics of the Azufre-Planchon-Peteroa volcanic complex, Chile

The Andean Southern Volcanic Zone (SVZ) is a vast and complex continental arc that has been studied extensively to provide an understanding of arc-magma genesis, the origin and chemical evolution of the continental crust, and geochemical compositions of volcanic products. The present study focuses on distinguishing the magma/sub-arc crustal interaction of eruptive products from the Azufre-Planchon-Peteroa (APP 35°15'S) volcanic center and other major centers in the Central SVZ (CSVZ 37°S–42°S), Transitional SVZ (TSVZ 34.3–37.0°S), and Northern SVZ (NSVZ 33°S–34°30'S). New Hf and Nd isotopic and trace element data for SVZ centers are consistent with former studies that these magmas experienced variable depths of crystal fractionation, and that crustal assimilation is restricted to the lower crustal depths with an apparent role of garnet. Thermobarometric calculations applied to magma compositions constrain the depth of magma separation from mantle sources in all segments of the SVZ to(70-90 km). Magmatic separation at the APP complex occurs at an average depth of ~50 km which is confined to the mantle lithosphere and the base of the crust suggesting localized thermal abrasion both reservoirs. Thermobarometric calculations indicate that CSVZ primary magmas arise from a similar average depth of (~54 km) which confines magma separation to the asthenospheric mantle. The northwards along-arc Sr-Nd-Hf isotopic data and LREE enrichment accompanied with HREE depletion of SVZ mafic magmas correlates well with northward increasing crustal thickness and decreasing primary melt separation from mantle source regions indicating an increased involvement of lower crustal components in SVZ magma petrogenesis. ^ The study concludes that the development of mature subduction zones over millions of years of continuous magmatism requires that mafic arc derived melts stagnate at lower crustal levels due to density similarities and emplace at lower crustal depths. Basaltic underplating creates localized hot zone environments below major magmatic centers. These regions of high temperature/partial melting, and equilibration with underplated mafic rocks provides the mechanism that controls trace element and isotopic variability of primary magmas of the TSVZ and NSVZ from their baseline CSVZ-like precursors.^