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At least 397 records · Page 22Linked to original sources

The influence of extractable organic matter on vitrinite reflectance suppression: A survey of kerogen and coal types

The vitrinite reflectance suppression literature shows that while bitumen impregnation of the vitrinite group is often invoked as a significant contributor to suppression, its existence is not often supported by petrological evidence. This study examines bitumen impregnation as a factor in vitrinite suppression by comparing the vitrinite reflectance of source rock and coal samples before and after solvent-extraction. Bitumen, often defined as organic matter soluble or extractable in certain organic solvents, should be removed by Soxhlet method solvent extraction using chloroform. Removing the extractable bitumen should restore the suppressed reflectance to its true higher value. However, the solvent extracted samples averaged 0.014% Rv less than that of the unextracted samples. We conclude from these results and from other published data that reflectance suppression by bitumen impregnation in the vitrinite maceral group, above the huminite stage of gelification, is seemingly a rare phenomenon and whose effect on suppressing vitrinite reflectance is typically negligible. ?? 2006.

International Journal of Coal Geology

Microscopical characterization of carbon materials derived from coal and petroleum and their interaction phenomena in making steel electrodes, anodes and cathode blocks for the Microscopy of Carbon Materials Working Group of the ICCP

This paper describes the evaluation of petrographic textures representing the structural organization of the organic matter derived from coal and petroleum and their interaction phenomena in the making of steel electrodes, anodes and cathode blocks. This work represents the results of the Microscopy of Carbon Materials Working Group in Commission III of the International Committee for Coal and Organic Petrology between the years 2009 and 2013. The round robin exercises were run on photomicrograph samples. For textural characterization of carbon materials the existing ASTM classification system for metallurgical coke was applied. These round robin exercises involved 15 active participants from 12 laboratories who were asked to assess the coal and petroleum based carbons and to identify the morphological differences, as optical texture (isotropic/anisotropic), optical type (punctiform, mosaic, fibre, ribbon, domain), and size. Four sets of digital black and white microphotographs comprising 151 photos containing 372 fields of different types of organic matter were examined. Based on the unique ability of carbon to form a wide range of textures, the results showed an increased number of carbon occurrences which have crucial role in the chosen industrial applications. The statistical method used to evaluate the results was based on the “raw agreement indices”. It gave a new and original view on the analysts' opinion by not only counting the correct answers, but also all of the knowledge and experience of the participants. Comparative analyses of the average values of the level of overall agreement performed by each analyst in the exercises during 2009–2013 showed a great homogeneity in the results, the mean value being 90.36%, with a minimum value of 83% and a maximum value of 95%.

International Journal of Coal Geology

Identification of alginite and bituminite in rocks other than coal. 2006, 2009, and 2011 round robin exercises of the ICCP Identification of Dispersed Organic Matter Working Group

The paper presents results of round robin exercises on photomicrograph-based identification of dispersed organic matter in source rocks that represent a range of marine and lacustrine deposits from worldwide localities and cover a range of thermal maturities. The round robin exercises were conducted by the Identification of Dispersed Organic Matter Working Group (IDOM WG) of the International Committee for Coal and Organic Petrology (ICCP). The round robin exercises aimed to (1) assess the applicability of the established ICCP definitions of bituminite, (2) identify deficiencies and improve the existing nomenclatures, and (3) provide a basis for the revision of the bituminite and alginite definitions in the ICCP Handbook (Taylor et al., 1998). Three round robin exercises performed in 2006, 2009 and 2011 involved 18 participants from research laboratories at universities and within government and industry. Participants were asked to identify macerals on the basis of existing definitions in 129 photomicrographs taken in incident white light and fluorescent mode and also in fluorescence light mode at prolonged (15 min) blue light irradiation. The results indicate that the definition of telalginite permits its positive and satisfactory agreement among the participants. In contrast, the descriptive characteristics of lamalginite referring to film-like appearance (filamentous) and lack of inner or outer structure are insufficient and inadequate to enable an unequivocal discrimination between it and telalginite. Furthermore, based on the amorphous nature of bituminite and lack of adherence to its established description and character (Taylor et al., 1998), the highest discrepancies were observed in its identification. Differentiation of bituminite from a fluorescent groundmass and in some cases from lamalginite proved to be particularly challenging. The findings of these round robin exercises are useful for improving the identification of sedimentary organic matter in source rocks and may be an important foundation for the modification of the ICCP definitions of alginite and bituminite.

International Journal of Coal Geology

On the petrographic distinction of bituminite from solid bitumen in immature to early mature source rocks

The oil-prone maceral bituminite (and its equivalents: ‘amorphous organic matter’, ‘sapropelinite’, ‘amorphinite’, etc.) converts to petroleum during thermal maturation of source rocks, resulting in formation of a mobile saturate-rich hydrocarbon and a polar-rich residue of solid bitumen. Evidence of this transition is preserved in immature to early mature source rocks (e.g., Alum, Bakken, Kimmeridge, New Albany, Ohio shales, among many others), where organic petrography reveals a continuum of textures, reflectance, and fluorescence intensity occurring between bituminite and solid bitumen. Bituminite generally is characterized by high(er) intensity fluorescence, low contrast to the inorganic matrix, lower reflectance (compared to solid bitumen), and heterogeneous wispy or ‘schlieren’ textures. In comparison, solid bitumen generally shows lower intensity or no fluorescence compared to bituminite, a distinct contrast to the mineral matrix which usually includes a gray homogeneous surface of low to moderate reflectance, and may possess void-filling, embayment or groundmass textures suggesting evidence of migration or its in situ exsolution. However, these properties may manifest across a continuous spectrum in a sample or in a single microscope field, often making identification inconclusive. Unambiguous identification is further hampered by sample preparation, e.g., mechanical polish may improve homogeneity of larger accumulations, whereas smaller accumulations, or those sheltered by hard minerals, may appear more heterogeneous, leading to identification of the same organic matter as solid bitumen or bituminite, respectively. The disruptive innovation of ion milling in shale sample preparation leads to increased organic reflectance and surface homogeneity, causing bituminite and other oil-prone macerals, e.g., alginite, to develop a gray reflecting surface which is easy to confuse with solid bitumen, especially when obvious void-filling or embayment textures of the latter are absent. Herein we review distinction of solid bitumen from bituminite and alginite in immature to early mature source rocks, providing examples from nine samples illustrated by typical organic petrography images, including samples from hydrous pyrolysis experiments. Based on a review of the literature, we observe an arbitrary reflectance limit of 0.30% in mechanically polished samples seems to differentiate bituminite (<0.30%) from confident identifications of homogeneous solid bitumen (which otherwise lacks obvious void-filling or identifying embayment textures) as individual macerals on a continuous spectrum in immature and early mature source rocks. Future work conducted by governing bodies such as the International Committee for Coal and Organic Petrology (ICCP) should consider interlaboratory studies conducted on multiple immature source rock samples to develop consensus guidelines for bituminite and solid bitumen discrimination.

International Journal of Coal Geology

Reflectance increase from broad beam ion milling of coals and organic-rich shales due to increased surface flatness

Broad ion beam (BIB) milling is useful in organic petrology because it can yield flat sample surfaces and avert the ‘smearing’ of organic matter (OM) that results from traditional mechanical polishing. This potentially makes BIB especially useful in the study of nano-porosity, where even minor mechanical disruption of the sample surface distorts the sample characteristic of interest—the pore structure. However, several studies have observed an OM reflectance increase after BIB milling, concluding that ion milling may cause thermal alteration to OM surfaces. To better understand ion milling effects on organic matter, coal (subbituminous, high volatile bituminous, medium volatile bituminous, anthracite) and shale [Bakken Formation, Ohio Shale-Huron Member (5), Kimmeridge Clay Formation, Alum Shale, New Albany Shale] samples were prepared using traditional mechanical polishing methods. Reflectance measurements (% Ro) were gathered on all maceral types present before BIB milling, followed by re-measurement of OM reflectance at the same locations after milling. Most OM increased in reflectance after BIB milling, with some exceptions in high maturity samples. Liptinite macerals in both coal and shale samples showed the greatest percent reflectance increase on average (+133%; n=338), followed by solid bitumen (+49%; n=313), vitrinite (+26%; n=413), and inertinite (+9%; n=220). Despite the increases to OM reflectance caused by BIB milling, no evidence was found for kerogen conversion (e.g., change in maceral abundances), or for migration of newly generated petroleum (e.g., pseudomorphic replacement of kerogen by solid bitumen). Such changes occur when samples are thermally altered from immature conditions into the oil window (e.g., by hydrous pyrolysis), and, if the increases in OM reflectance were thermally driven (by BIB milling), they should have been observed in the above experiments. Herein, we also used atomic force microscopy to document a decrease in surface roughness of correlative locations of OM on pre- and post-ion milled samples. This improved surface polish caused by BIB milling appears to be the root cause of increased OM reflectance, as no other supporting evidence of thermal alteration could be found. That is, the fraction of light formerly lost to oblique scatter in diffuse reflectance from a mechanically polished surface is converted to specular reflectance after BIB ion milling. Thus the light leaves the surface at a near normal angle and returns to the detector, resulting in increased OM reflectance.

International Journal of Coal Geology

Application of electron microscopy TEM and SEM for analysis of coals, organic-rich shales and carbonaceous matter

This paper provides a brief summary of the history, development and variety of applications of electron microscopy techniques to analyze coals, organic-rich shales, and carbonaceous materials. General construction and principles of operation of transmitted (TEM) and scanning electron microscope (SEM) are outlined, along with guidance on specimen preparation, and a brief overview of published TEM and SEM applications related to coal, shales, and carbonaceous materials. This work was accepted as the chapter 18.2 of International Committee for Coal and Organic Petrology Methods Handbook at the ICCP Plenary Session on September 27, 2018 in Brisbane (Australia).

International Journal of Coal Geology

A review of spatially resolved techniques and applications of organic petrography in shale petroleum systems

This review examines new techniques and applications of organic petrography in source-rock reservoir petroleum systems that have occurred along with development of the global ‘shale revolution’ in energy resources. The review is limited to techniques and instrumentation that provide spatially resolved information, typically at or below microscales, for dispersed organic matter occurring in situ in samples of shale and mudrock. A brief summary of ion beam sample preparation is followed by discussion of the most common analytical techniques and applications. Advantages and limitations of each technique, including requisite sample preparation, types of information generated [e.g., molecular or elemental (isotopic) abundance], sensitivity, and resolution are discussed. In a few cases, techniques not yet applied to organic petrology of shale or mudrock are described (e.g., X-ray photoelectron spectroscopy imaging), in anticipation of near-term future application. The most common in situ techniques applied for characterization of organic matter in shale and mudrock include optical (including fluorescence) and electron microscopies, Raman, fluorescence, and infrared spectroscopies, and surficial measurements via force microscopy. Techniques that show growing application to organic petrography of shale include tip-enhanced photothermal infrared spectroscopy, mass spectrometry imaging, and synchrotron-based spectroscopies, among others. It is anticipated that the future of dispersed organic matter petrography will hold continued development of integrated instrument techniques (e.g., simultaneous or sequential correlative microscopies and/or spectroscopies of the same location), increased instrumental resolution, increased use of multiscale and multimodal organic petrography investigations, and three-dimensional imaging and chemical speciation mapping applications via multiple analytical approaches.

International Journal of Coal Geology

Structure and morphology of chars and activated carbons obtained from thermal treatment of coal and biomass origin materials, including their wastes: Results from the ICCP Microscopy of Carbon Materials Working Group

This paper describes the evaluation of petrographic textures in char and activated carbon derived from coal, coal by-products and biomass, formed during carbonization and activation processes. This work represents the results of interlaboratory exercises from 2016 to 2022 of the Microscopy of Carbon Materials Working Group in Commission III of the International Committee for Coal and Organic Petrology. The interlaboratory exercises were run on photomicrograph samples. For textural characterization of carbon materials, the existing American Society for Testing and Materials (ASTM) classification system for metallurgical coke was applied. Morphological differences were evaluated in 29 carbon material types, including 22 char samples, and 7 activated carbon (AC) samples obtained experimentally using conventional direct/indirect and microwave heating technologies. This approach gives an extended view on the identification of microporous carbons, and how a certain heat treatment develops a certain optical texture and structure in a raw material. The requested evaluation of carbon materials was related to their porosity, origin, extent, and characteristics, which are particular to each carbon material type. Because carbon matrices can form a wide range of optical textures during heat treatment it is important to demonstrate which carbon occurrences will have a crucial role in industrial applications dominated by adsorption phenomena. The interlaboratory exercises included 17 participants from 14 laboratories. Four sets of digital black and white and colour photomicrographs were distributed, which in total comprised 184 fields of different types of carbon material. The results were evaluated based on four levels: (i) optical texture (isotropic/anisotropic), (ii) optical type and size (punctiform, mosaic, fiber, ribbon, domain), iii) morphology (porous, non-porous/massive), and (iv) particle origin (precursor type). The statistical method applied to evaluate the results was based on “raw agreement indices”. Comparative analyses of the average values of the level of overall agreement showed homogeneity in the results, the mean value was 89%, with a minimum value of 87% and a maximum value of 91% for those who participated in at least three out of four exercises.

International Journal of Coal Geology

Confocal laser-scanning microscopy (CLSM)-based thermal maturity of Tasmanites and progress in standardization of fluorescence microspectrometry

Evaluation of thermal maturity in vitrinite-free or vitrinite-deficient sediments via fluorescence microspectrometry can provide relevant information related to petroleum exploration and thermal history assessment. However, variation in spectral fluorescence properties of alginite macerals with increasing thermal maturity is largely underexplored. Here, authors of this study have applied confocal laser-scanning microscopy (CLSM) in conjunction with fluorescence microspectrometry to a maturity series of marine Upper Devonian Tasmanites algae from the Ohio Shale (Huron Member) and a single sample from the Marcellus Formation of the Appalachian Basin. Spectral fluorescence properties of Tasmanites were evaluated in relation to orientation, measurement location, and the number of measurements per sample, and were compared to published literature. Emission spectra of Tasmanites from continuous wave laser excitation (405 nm) were acquired from sections perpendicular and parallel to bedding and at different positions within individual Tasmanites bodies. The results showed a progressive red-shift in emission maxima (λ max ) in a large sample sized maturity series ( N = 19), e.g., 493 to 578 nm for the perpendicular section at middle position. Further, blue-shifted apex and mineral-adjacent positions within sections perpendicular to bedding were observed, with the latter being reported here for the first time. While blue-shift at apex positions can be attributed to mechanical deformation-induced reorientation of photoselected fluorophores, the blue-shifted mineral-adjacent positions could result from strain loading and development of a plastic deformation region at the mineral contact zone with Tasmanites . A decrease in standard deviation with increasing number of measured emission maxima is well-observed, and 15 to 20 individual measurements per sample appears sufficient for low standard deviation and coefficient of variance. CLSM-derived thermal maturity parameters indicated that a moderate positive correlation of red/green quotient (Q 650/500 ; R 2 = 0.67) with solid bitumen reflectance (BR o in %) exists. For reproducible results, the determination of λ max and Q 650/500 should be conducted exclusively in the middle position at perpendicular and parallel sections of the polished whole-rock pellets, where the lowest standard deviation in measurement was observed. These results strengthen the suitability and relevance of the CLSM technique in thermal maturity studies of dispersed organic matter (DOM) and contribute to the standardization of fluorescence microspectrometry methods in organic petrology investigation.

Kentucky, Ohio, Virginia, West Virginia

Diffusion-driven magnesium and iron isotope fractionation in Hawaiian olivine

Diffusion plays an important role in Earth sciences to estimate the timescales of geological processes such as erosion, sediment burial, and magma cooling. In igneous systems, these diffusive processes are recorded in the form of crystal zoning. However, meaningful interpretation of these signatures is often hampered by the fact that they cannot be unambiguously ascribed to a single process (e.g., magmatic fractionation, diffusion limited transport in the crystal or in the liquid). Here we show that Mg and Fe isotope fractionations in olivine crystals can be used to trace diffusive processes in magmatic systems. Over sixty olivine fragments from Hawaiian basalts show isotopically fractionated Mg and Fe relative to basalts worldwide, with up to 0.4‰ variation in 26 Mg/ 24 Mg ratios and 1.6‰ variation in 56 Fe/ 54 Fe ratios. The linearly and negatively correlated Mg and Fe isotopic compositions [i.e., δ 56 Fe = (− 3.3 ± 0.3) × δ 26 Mg], co-variations of Mg and Fe isotopic compositions with Fe/Mg ratios of olivine fragments, and modeling results based on Mg and Fe elemental profiles demonstrate the coupled Mg and Fe isotope fractionation to be a manifestation of Mg–Fe inter-diffusion in zoned olivines during magmatic differentiation. This characteristic can be used to constrain the nature of mineral zoning in igneous and metamorphic rocks, and hence determine the residence times of crystals in magmas, the composition of primary melts, and the duration of metamorphic events. With improvements in methodology, in situ isotope mapping will become an essential tool of petrology to identify diffusion in crystals.

Hawaii

The effect of pressurized magma chamber growth on melt migration and pre-caldera vent locations through time at Mount Mazama, Crater Lake, Oregon

The pattern of eruptions at long-lived volcanic centers provides a window into the co-evolution of crustal magma transport, tectonic stresses, and unsteady magma generation at depth. Mount Mazama in the Oregon Cascades has seen variable activity over the last 400 ky, including the 50 km 3 climactic eruption at ca. 7.7 ka that produced Crater Lake caldera. The physical mechanisms responsible for the assembly of silicic magma reservoirs that are the precursors to caldera-forming eruptions are poorly understood. Here we argue that the spatial and temporal distribution of geographically clustered volcanic vents near Mazama reflects the development of a centralized magma chamber that fed the climactic eruption. Time-averaged eruption rates at Mount Mazama imply an order of magnitude increase in deep magma influx prior to the caldera-forming event, suggesting that unsteady mantle melting triggered a chamber growth episode that culminated in caldera formation. We model magma chamber&ndash;dike interactions over &sim;50 ky preceding the climactic eruption to fit the observed distribution of surface eruptive vents in space and time, as well as petrologically estimated deep influx rates. Best fitting models predict an expanding zone of dike capture caused by a growing, oblate spheroidal magma chamber with 10&ndash;30 MPa of overpressure. This growing zone of chamber influence causes closest approaching regional mafic vent locations as well as more compositionally evolved Mazama eruptions to migrate away from the climactic eruptive center, returning as observed to the center after the chamber drains during the caldera-forming eruption.

Oregon

Ultramafic float rocks at Jezero crater (Mars): Excavation of lower crustal rocks or mantle peridotites by impact cratering?

Based on observation and data from meteorites and in situ scientific missions, experiments as well as models, the Martian mantle is assumed to share some compositional and mineralogical affinity with the terrestrial mantle. However, there might be subtle differences like the Martian mantle being more ferroan. Yet, we do not have any direct analysis of a Martian mantle rock to confirm this assumption. NASA’s Perseverance rover found olivine-rich boulder-sized float rocks on the upper Jezero fan (Mars). These boulders have an ultramafic composition and their mineralogy is dominantly composed of Fo 73±3 olivine with high-Mg orthopyroxene, Cr-rich Ti-Fe oxides and minor plagioclase and high-Ca pyroxene. Microtextural and petrological analysis reveals that these minerals crystallized at equilibrium. In addition, these boulders are different from all the bedrocks analyzed by Perseverance along its traverse which are crustal igneous rocks and sediments. Comparing our data to Martian meteorites and available Mars bulk silicate models (BSM), we discuss that these boulders could represent primitive melts and/or lower crustal material, and we specifically hypothesize that they could be mantle peridotites. We propose that these putative mantle rocks could have been excavated by the succession of impacts from the shallow mantle or lower crust in the Isidis region where Jezero crater is located. These olivine-rich boulders could thereby constitute the first direct analysis of a Martian mantle rock.

Earth and Planetary Science Letters

Recycling radiogenic osmium by crustal foundering in subduction zones: Evidence from pyroxenite xenoliths in the north Andean arc

Removal of mafic-ultramafic lower crust (e.g., via delamination) is fundamental to making andesitic continental crust, yet direct evidence of this process remains elusive. A unique suite of garnet clinopyroxenite and hornblendite (arclogite) xenoliths from the northern volcanic zone of the Andes, erupted to the surface in the mid-Pleistocene, have bulk-rock geochemistry and osmium (Os) isotopic compositions that demonstrate their crustal affinity, yet have equilibration pressures and temperatures below the arc Mohorovičić discontinuity (~53 km) and some as deep as within the sub-arc mantle wedge (~105 km). Garnet websterites from the same xenolith suite, sourced from depths approaching the Wadati-Benioff zone (~140 km), have elemental and isotopic compositions indicative of a mantle origin, likely formed as products of peridotite-liquid reactions above the subducting slab. Variability in bulk-rock 143 Nd/ 144 Nd values and garnet oxygen isotope ratios ( 𝛿 18 O) for these samples is attributed to minor assimilation of subducted components and/or older crustal material, but assimilation alone cannot account for the highly radiogenic Os isotopic compositions. These results provide direct petrologic evidence for modern arclogite formation and foundering in the Andean orogen, the archetypal active continental subduction system. Elevated 187 Os/ 188 Os values of Mercaderes arclogites imply that recycling of gravitationally unstable arc cumulates during continental crust formation introduces highly radiogenic Os into the convective mantle, which has implications for mass fluxes across the crust-mantle boundary as well as the sources and evolution of mantle heterogeneity as seen in orogenic peridotite massifs and in the sources of oceanic basalts

Earth and Planetary Science Letters

Discerning crystal growth from diffusion profiles in zoned olivine by in situ Mg–Fe isotopic analyses

Mineral zoning is used in diffusion-based geospeedometry to determine magmatic timescales. Progress in this field has been hampered by the challenge to discern mineral zoning produced by diffusion from concentration gradients inherited from crystal growth. A zoned olivine phenocryst from Kilauea Iki lava lake (Hawaii) was selected for this study to evaluate the potential of Mg and Fe isotopes for distinguishing these two processes. Microdrilling of the phenocryst (∼300 μm drill holes) followed by MC-ICPMS analysis of the powders revealed negatively coupled Mg and Fe isotopic fractionations (δ 26 Mg from +0.1‰ to −0.2‰ and δ 56 Fe from −1.2‰ to −0.2‰ from core to rim), which can only be explained by Mg–Fe exchange between melt and olivine. The data can be explained with ratios of diffusivities of Mg and Fe isotopes in olivine scaling as D 2 /D 1 = (m 1 /m 2 )β with β Mg ∼0.16 and β Fe ∼0.27. LA-MC-ICPMS and MC-SIMS Fe isotopic measurements are developed and are demonstrated to yield accurate δ 56 Fe measurements within precisions of ∼0.2‰ (1 SD) at spatial resolutions of ∼50 μm. δ 56 Fe and δ 26 Mg stay constant with Fo# in the rim (late-stage overgrowth), whereas in the core (original phenocryst) δ 56 Fe steeply trends toward lighter compositions and δ 26 Mg trends toward heavier compositions with higher Fo#. A plot of δ 56 Fe vs. Fo# immediately distinguishes growth-controlled from diffusion-controlled zoning in these two regions. The results are consistent with the idea that large isotopic fractionation accompanies chemical diffusion in crystals, whereas fractional crystallization induces little or no isotopic fractionation. The cooling timescale inferred from the chemical-isotope zoning profiles is consistent with the documented cooling history of the lava lake. In the absence of geologic context, in situ stable isotopic measurements may now be used to interpret the nature of mineral zoning. Stable isotope measurements by LA-MC-ICPMS and MC-SIMS can be used as standard petrologic tools to identify samples for diffusion-based geospeedometry.

Geochimica et Cosmochimica Acta

Zircon-hosted melt inclusion record of silicic magmatism in the Mesoproterozoic St. Francois Mountains terrane, Missouri: Origin of the Pea Ridge iron oxide-apatite rare earth element deposit and implications for regional crustal pathways of mineralization

Voluminous silicic magmatism was coeval with iron ore mineralization in the St. Francois Mountains terrane in southeast Missouri, part of the broader Mesoproterozoic Granite-Rhyolite province along the eastern margin of Laurentia. Some of the iron deposits contain extraordinary endowments of critical elements, such as the Pea Ridge iron oxide-apatite (IOA) deposit, which has an average grade of ~12 wt% rare earth oxides in breccia pipes that flank the ore body. To assess the role of silicic magmatism in the genesis of the Pea Ridge deposit, we present a high-spatial resolution study of zirconhosted melt inclusions from rhyolitic ash-flow tuffs. Melt inclusion data are combined with textural, geochemical, and geochronological analyses of zircon hosts to elucidate the magmatic-hydrothermal evolution of the Pea Ridge system. Two contemporaneous silicic igneous centers in the St. Francois Mountains terrane, Bourbon and Eminence, were studied for comparison. Pea Ridge melt inclusions are trachydacitic to rhyolitic (~63-79 wt% SiO2, ~5.6-11.7 wt% Na2O+K2O) with very high Cl in the least-evolved and most alkaline melt inclusions (~2,000-5,000 ppm Cl). Rare earth elements (REE) in melt inclusions have identical chondrite-normalized patterns to the mineralized breccia pipes, but with systematically lower absolute concentrations. Haplogranite ternary pressures range from ~0.5-10 kbar, with an average of ~2-3 kbar (7-12 km depth), and liquidus temperatures are ~850-950 °C, with an average of ~920 °C. Silicate and phosphate mineral inclusions have compositions that overlap minerals from the iron ore body and breccia pipes, recording a transition from igneous to hydrothermal zircon growth. Igneous iron oxide inclusions have compositions that indicate Pea Ridge magmas were reduced to moderately oxidized (log fO2 of -0.8 to -1.84 NNO). Zircons from two Pea Ridge samples have 207Pb/206Pb concordia ages of 1456 ± 9 Ma and 1467 ± 13 Ma that overlap published ages for the breccia pipes and iron ore zones of the Pea Ridge deposit. A population of texturally and chemically disrupted zircons have discordant domains that correspond to high Fe, U, and REE concentrations, consistent with the unique geochemical attributes of the IOA-REE ore body. Inherited cores in Pea Ridge and Bourbon zircons have concordant 207Pb/206Pb dates of 1550-1618 Ma, providing direct evidence of cratonic basement beneath these centers. Oxygen isotope data for inherited and autocrystic igneous zircons span from mantle to crustal values (18Ozircon=5.5-7.9‰). Our data are consistent with a model in which metasomatized mantle components were mixed with cratonic and accreted crustal material in a back-arc or rifted segment of a volcanic arc, with ore fluids derived from Cl-rich melts to transport Fe and REE in a long-lived (tens of Myr), pulsed, magmatic-hydrothermal system. Bourbon, which also possesses IOA mineralization, shares key petrologic similarities with the Pea Ridge system, whereas Eminence, which is not mineralized, has disparate geochemical and isotopic signatures that indicate it formed in a different crustal setting. The location of Pea Ridge and Bourbon along a cratonic margin may have been important in focusing silicic melts and mineralization in the upper crust, serving as a guide for future exploration efforts.

Missouri

The 2010 explosive eruption of Java's Merapi volcano—A ‘100-year’ event

Merapi volcano (Indonesia) is one of the most active and hazardous volcanoes in the world. It is known for frequent small to moderate eruptions, pyroclastic flows produced by lava dome collapse, and the large population settled on and around the flanks of the volcano that is at risk. Its usual behavior for the last decades abruptly changed in late October and early November 2010, when the volcano produced its largest and most explosive eruptions in more than a century, displacing at least a third of a million people, and claiming nearly 400 lives. Despite the challenges involved in forecasting this ‘hundred year eruption’, we show that the magnitude of precursory signals (seismicity, ground deformation, gas emissions) was proportional to the large size and intensity of the eruption. In addition and for the first time, near-real-time satellite radar imagery played an equal role with seismic, geodetic, and gas observations in monitoring eruptive activity during a major volcanic crisis. The Indonesian Center of Volcanology and Geological Hazard Mitigation (CVGHM) issued timely forecasts of the magnitude of the eruption phases, saving 10,000–20,000 lives. In addition to reporting on aspects of the crisis management, we report the first synthesis of scientific observations of the eruption. Our monitoring and petrologic data show that the 2010 eruption was fed by rapid ascent of magma from depths ranging from 5 to 30 km. Magma reached the surface with variable gas content resulting in alternating explosive and rapid effusive eruptions, and released a total of ~ 0.44 Tg of SO 2 . The eruptive behavior seems also related to the seismicity along a tectonic fault more than 40 km from the volcano, highlighting both the complex stress pattern of the Merapi region of Java and the role of magmatic pressurization in activating regional faults. We suggest a dynamic triggering of the main explosions on 3 and 4 November by the passing seismic waves generated by regional earthquakes on these days.

Merapi volcano

Quantification of the intrusion process at Kīlauea volcano, Hawai'i

The characteristic size of two types of intrusions identified beneath Kīlauea's East Rift zone are uniquely estimated by combining time constraints from fractional crystallization and the rates of magma solidification during cooling. Some intrusions were rapidly emplaced as dikes, but stalled before reaching the surface, and cooled and crystallized to feed later fractionated eruptions. More specifically, using the observed time interval between initial emplacement and eruption of fractionated lava, whose degree of fractionation is estimated from petrologic mixing calculations, the extent of solidification or cooling needed to produce this amount of fractionation can be directly inferred. And from the known erupted volumes the spatial extent or size of this fractionated volume can be analytically related to the full size of the source body itself. Two examples yield dike widths of 82 and 68 m. Other intrusions remain close to the east rift magma transport path and are observed to last for decades or longer as viable magma bodies that may participate in feeding later eruptions. The thickness of semi-permanent reservoirs near the East Rift Zone magma transport path can be estimated by assuming a resupply rate that is sufficiently frequent to restrict cooling to < 10 °C. It is inferred that both types of intrusions likely began as dike offshoots from the East Rift Zone magma transport path, but the frequently resupplied bodies may have later been converted to sills or laccoliths of heights estimated at 43–62 m. Our modeled intrusions contrast with models of rapidly emplaced thinner dikes feeding shallow intrusions, which are accompanied by intense rift earthquake swarms and are often associated with eruptions. These calculations show that long-term heating of the wallrock of the magma transport paths serves to slow conduit cooling, which may be partly responsible for sustaining long East Rift Zone eruptions. Adjacent to the vertical transport path beneath Kīlauea's summit, the combined effects of heating and ever-increasing magma supply rate may have forced a commensurate enlarging of the conduit, perhaps explaining the occurrence of a temporary burst of deep (5–15 km) long-period earthquake swarms between 1987 and 1992.

Hawaii

Juvenile magma recognition and eruptive dynamics inferred from the analysis of ash time series: The 2015 reawakening of Cotopaxi volcano

Forecasting future activity and performing hazard assessments during the reactivation of volcanoes remain great challenges for the volcanological community. On August 14, 2015 Cotopaxi volcano erupted for the first time in 73 years after approximately four months of precursory activity, which included an increase in seismicity, gas emissions, and minor ground deformation. Here we discuss the use of near real-time petrological monitoring of ash samples as a complementary aid to geophysical monitoring, in order to infer eruption dynamics and evaluate possible future eruptive activity at Cotopaxi. Twenty ash samples were collected between August 14 and November 23, 2015 from a monitoring site on the west flank of the volcano. These samples contain a range of grain types that we classified as: hydrothermal/altered, lithic, juvenile, and free crystals. The relative proportions of theses grains evolved as the eruption progressed, with increasing amounts of juvenile material and a decrease in hydrothermally altered material. In samples from the initial explosion, juvenile grains are glassy, microlite-poor and contain hydrothermal minerals (opal and alunite). The rising magma came in contact with the hydrothermal system under confinement, causing hydro-magmatic explosions that cleared the upper part of the plumbing system. Subsequently, the magmatic column produced a thermal aureole in the conduit and dried out the hydrothermal system, allowing for dry eruptions. Magma ascent rates were low enough to allow for efficient outgassing and microlite growth. Constant supply of magma from below caused quasi-continuous disruption of the uppermost magma volume through a combination of shear-deformation and gas expansion. The combination of increasing crystallinity of juvenile grains, and high measured SO 2 flux indicate decreasing integrated magma ascent rates and clearing of the hydrothermal system along transport pathways in a system open to gas loss. The near real-time monitoring of ash samples combined with traditional geophysical monitoring techniques during the reawakening of Cotopaxi allowed us to gain a much clearer understanding of events than when using traditional geophysical monitoring alone.

Cotopaxi volcano