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1. Comparison of secondary organic aerosol generated from the oxidation of laboratory precursors by hydroxyl radicals, chlorine atoms, and bromine atoms in an oxidation flow reactor

   https://doi.org/10.1039/D2EA00018K  

   Lambe, Andrew T. ; Avery, Anita M. ; Bhattacharyya, Nirvan ; Wang, Dongyu S. ; Modi, Mrinali ; Masoud, Catherine G. ; Ruiz, Lea Hildebrandt ; Brune, William H. ( July 2022 , Environmental Science: Atmospheres)

   The role of hydroxyl radicals (OH) as a daytime oxidant is well established on a global scale. In specific source regions, such as the marine boundary layer and polluted coastal cities, other daytime oxidants, such as chlorine atoms (Cl) and even bromine atoms (Br), may compete with OH for the oxidation of volatile organic compounds (VOCs) and/or enhance the overall oxidation capacity of the atmosphere. However, the number of studies investigating halogen-initiated secondary organic aerosol (SOA) formation is extremely limited, resulting in large uncertainties in these oxidative aging processes. Here, we characterized the chemical composition and yield of laboratory SOA generated in an oxidation flow reactor (OFR) from the OH and Cl oxidation of n -dodecane ( n -C 12 ) and toluene, and the OH, Cl, and Br oxidation of isoprene and α-pinene. In the OFR, precursors were oxidized using integrated OH, Cl, and Br exposures ranging from 3.1 × 10 10 to 2.3 × 10 12 , 6.1 × 10 9 to 1.3× 10 12 and 3.2 × 10 10 to 9.7 × 10 12 molecules cm −3 s −1 , respectively. Like OH, Cl facilitated multistep SOA oxidative aging over the range of OFR conditions that weremore »studied. In contrast, the extent of Br-initiated SOA oxidative aging was limited. SOA elemental ratios and mass yields obtained in the OFR studies were comparable to those obtained from OH and Cl oxidation of the same precursors in environmental chamber studies. Overall, our results suggest that alkane, aromatic, and terpenoid SOA precursors are characterized by distinct OH- and halogen-initiated SOA yields, and that while Cl may enhance the SOA formation potential in regions influenced by biogenic and anthropogenic emissions, Br may have the opposite effect.« less
2. D/H ratios and H2O contents record degassing and rehydration history of rhyolitic magma and pyroclasts

   Thomas Giachetti, Michael R.Hudak ( January 2019 , Earth and planetary science letters)

   Volcanic eruptions of rhyolitic magma often show shifts from powerful (Vulcanian to Plinian) explosive episodes to a more gentle effusion of viscous lava forming obsidian flows. Another prevailing characteris-tic of these eruptions is the presence of pyroclastic obsidians intermingled with the explosive tephra. This dense, juvenile product is similar to the tephra and obsidian flow in composition, but is generally less degassed than its flow counterpart. The formation mechanism(s) of pyroclastic obsidians and the information they can provide concerning the extent to which magma degassing modulates the eruptive style of rhyolitic eruptions are currently subject to active research. Porous tephra and pyroclastic and flow obsidians from the 1060CE Glass Mountain rhyolitic eruption at Medicine Lake Volcano (California) were analyzed for their porosity, φ, water content, H2O, and hydrogen isotopic composition, δD. H2O in porous pyroclasts is correlated negatively with δD and positively with φ, indicating that the samples were affected by post-eruptive rehydration. Numerical modeling suggests that this rehydration occurred at an average rate of 10−23.5±0.5m2s−1during the ∼960 years since the eruption, causing some pyroclasts to gain up to 1 wt%of meteoric water. Pyroclastic and flow obsidians were not affected by rehydration due to their very low porosity. Comparison betweenmore »modeled δD-H2O relationships in degassing magma and values measured in the Glass Mountain samples supports the idea that rhyolitic magma degasses in closed-system until its porosity reaches a value of about 65±5%, beyond which degassing occurs in open-system until quench. During the explosive phase, rapidly ascending magma fragments soon after it becomes permeable, creating porous lapilli and ash that continue to degas in open-system within an expanding gas phase. As suggested by recent studies, some ash may aggregate and sinter on the conduit sides at different depths above the fragmentation level, partly equilibrating with the continuously fluxing heavier magmatic vapor, explaining the wide range of H2O contents and high variability in δD measured in the pyroclastic obsidians. Using only H2O and δD, it is impossible to rule out the possibility that pyroclastic obsidians may also form by permeable foam collapse, either syn-explosively near the conduit sides below the fragmentation level or during more effusive periods interspersed in the explosive phase. During the final effusive phase of the eruption, slowly ascending magma degasses in open-system until it reaches the surface, creating flows with low H2O and δD. This study shows that H2O measured in highly porous pyroclasts of a few hundred years or more cannot be used to infer syn-eruptive magma degassing pathways, unless careful assessment of post-eruptive rehydration is first carried out. If their mechanism of formation can be better understood, detailed analysis of the variations in texture and volatile content of pyroclastic obsidians throughout the explosive phase may help decipher the reasons why rhyolitic eruptions commonly shift from explosive to effusive phases.« less
3. Mush, Melts and Metasediments: a History of Rhyolites from the Okataina Volcanic Centre, New Zealand, as Captured in Plagioclase

   https://doi.org/10.1093/petrology/egab038  

   Sas, May ; Shane, Phil ; Kuritani, Takeshi ; Zellmer, Georg F ; Kent, Adam J ; Nakagawa, Mitsuhiro ( August 2021 , Journal of Petrology)

   Abstract The Okataina Volcanic Centre (OVC), located in the Taupo Volcanic Zone, New Zealand, is a dominantly rhyolitic magmatic system in an arc setting, where eruptions are thought to be driven by mafic recharge. Here, Sr–Pb isotopes, and compositional and textural variations in plagioclase phenocrysts from 10 rhyolitic deposits (two caldera, one immediately post-caldera, four intra-caldera, and three extra-caldera) are used to investigate the OVC magmatic system and identify the sources and assimilants within this diverse mush zone. Plagioclase interiors exhibit normal and reverse zoning, and are commonly in disequilibrium with their accompanying glass, melt inclusions, and whole-rock compositions. This indicates that the crystals nucleated in melts that differed from their carrier magma. In contrast, the outermost rims of crystals exhibit normal zoning that is compositionally consistent with growth in cooling and fractionating melts just prior to eruption. At the intra-crystal scale, the total suite of 87Sr/86Sr ratios are highly variable (0·7042–0·7065 ± 0·0004 average 2SE); however, the majority (95 %) of the crystals are internally homogeneous within error. At whole-crystal scale (where better precision is obtained), 87Sr/86Sr ratios are much more homogeneous (0·70512–0·70543 ± 0·00001 average 2SE) and overlap with their host whole-rock Sr isotopic ratios. Whole-crystal Pb isotopic ratios also largely overlap withmore »whole-rock Pb ratios. The plagioclase and whole-rock isotopic compositions indicate significant crustal assimilation (≥20 %) of Torlesse-like metasediments (local basement rock) by a depleted mid-ocean ridge mantle magma source, and Pb isotopes require variable fluid-dominant subduction flux. The new data support previous petrogenetic models for OVC magmas that require crystal growth in compositionally and thermally distinct magmas within a complex of disconnected melt-and-mush reservoirs. These reservoirs were rejuvenated by underplating basaltic magmas that serve as an eruption trigger. However, the outermost rims of the plagioclase imply that interaction between silicic melts and eruption-triggering mafic influx is largely limited to heat and volatile transfer, and results in rapid mobilization and syn-eruption mixing of rhyolitic melts. Finally, relatively uniform isotopic compositions of plagioclase indicate balanced contributions from the crust and mantle over the lifespan of the OVC magmatic system.« less
4. One hundred years of advances in volcano seismology and acoustics

   https://doi.org/10.1007/s00445-022-01586-0  

   Matoza, Robin S. ; Roman, Diana C. ( August 2022 , Bulletin of Volcanology)

   Since the 1919 foundation of the International Association of Volcanology and Chemistry of the Earth’s Interior (IAVCEI), the fields of volcano seismology and acoustics have seen dramatic advances in instrumentation and techniques, and have undergone paradigm shifts in the understanding of volcanic seismo-acoustic source processes and internal volcanic structure. Some early twentieth-century volcanological studies gave equal emphasis to barograph (infrasound and acoustic-gravity wave) and seismograph observations, but volcano seismology rapidly outpaced volcano acoustics and became the standard geophysical volcano-monitoring tool. Permanent seismic networks were established on volcanoes (for example) in Japan, the Philippines, Russia, and Hawai‘i by the 1950s, and in Alaska by the 1970s. Large eruptions with societal consequences generally catalyzed the implementation of new seismic instrumentation and led to operationalization of research methodologies. Seismic data now form the backbone of most local ground-based volcano monitoring networks worldwide and play a critical role in understanding how volcanoes work. The computer revolution enabled increasingly sophisticated data processing and source modeling, and facilitated the transition to continuous digital waveform recording by about the 1990s. In the 1970s and 1980s, quantitative models emerged for long-period (LP) event and tremor sources in fluid-driven cracks and conduits. Beginning in the 1970s, early models formore »volcano-tectonic (VT) earthquake swarms invoking crack tip stresses expanded to involve stress transfer into the wall rocks of pressurized dikes. The first deployments of broadband seismic instrumentation and infrasound sensors on volcanoes in the 1990s led to discoveries of new signals and phenomena. Rapid advances in infrasound technology; signal processing, analysis, and inversion; and atmospheric propagation modeling have now established the role of regional (15–250 km) and remote (> 250 km) ground-based acoustic systems in volcano monitoring. Long-term records of volcano-seismic unrest through full eruptive cycles are providing insight into magma transport and eruption processes and increasingly sophisticated forecasts. Laboratory and numerical experiments are elucidating seismo-acoustic source processes in volcanic fluid systems, and are observationally constrained by increasingly dense geophysical field deployments taking advantage of low-power, compact broadband, and nodal technologies. In recent years, the fields of volcano geodesy, seismology, and acoustics (both atmospheric infrasound and ocean hydroacoustics) are increasingly merging. Despite vast progress over the past century, major questions remain regarding source processes, patterns of volcano-seismic unrest, internal volcanic structure, and the relationship between seismic unrest and volcanic processes.

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5. Mafic explosive volcanism at Llaima Volcano: 3D x-ray microtomography reconstruction of pyroclasts to constrain shallow conduit processes

   https://doi.org/10.1007/s00445-021-01514-8  

   Valdivia, Pedro ; Marshall, Aaron A. ; Brand, Brittany D. ; Manga, Michael ; Huber, Christian ( December 2021 , Bulletin of Volcanology)

   Mafic volcanic activity is dominated by effusive to mildly explosive eruptions. Plinian and ignimbrite-forming mafic eruptions, while rare, are also possible; however, the conditions that promote such explosivity are still being explored. Eruption style is determined by the ability of gas to escape as magma ascends, which tends to be easier in low-viscosity, mafic magmas. If magma permeability is sufficiently high to reduce bubble overpressure during ascent, volatiles may escape from the magma, inhibiting violent explosive activity. In contrast, if the permeability is sufficiently low to retain the gas phase within the magma during ascent, bubble overpressure may drive magma fragmentation. Rapid ascent may induce disequilibrium crystallization, increasing viscosity and affecting the bubble network with consequences for permeability, and hence, explosivity. To explore the conditions that promote strongly explosive mafic volcanism, we combine microlite textural analyses with synchrotron x-ray computed microtomography of 10 pyroclasts from the 12.6 ka mafic Curacautín Ignimbrite (Llaima Volcano, Chile). We quantify microlite crystal size distributions (CSD), microlite number densities, porosity, bubble interconnectivity, bubble number density, and geometrical properties of the porous media to investigate the role of magma degassing processes at mafic explosive eruptions. We use an analytical technique to estimate permeability and tortuosity bymore »combing the Kozeny-Carman relationship, tortuosity factor, and pyroclast vesicle textures. The groundmass of our samples is composed of up to 44% plagioclase microlites, > 85% of which are < 10 µm in length. In addition, we identify two populations of vesicles in our samples: (1) a convoluted interconnected vesicle network produced by extensive coalescence of smaller vesicles (> 99% of pore volume), and (2) a population of very small and completely isolated vesicles (< 1% of porosity). Computed permeability ranges from 3.0 × 10⁻¹³to 6.3 × 10⁻¹²m², which are lower than the similarly explosive mafic eruptions of Tarawera (1886; New Zealand) and Etna (112 BC; Italy). The combination of our CSDs, microlite number densities, and 3D vesicle textures evidence rapid ascent that induced high disequilibrium conditions, promoting rapid syn-eruptive crystallization of microlites within the shallow conduit. We interpret that microlite crystallization increased viscosity while simultaneously forcing bubbles to deform as they grew together, resulting in the permeable by highly tortuous network of vesicles. Using the bubble number densities for the isolated vesicles (0.1-3⁻³ × 10⁴ bubbles per mm³), we obtain a minimum average decompression rate of 1.4 MPa/s. Despite the textural evidence that the Curacautín magma reached the percolation threshold, we propose that rapid ascent suppressed outgassing and increased bubble overpressures, leading to explosive fragmentation. Further, using the porosity and permeability of our samples, we estimated that a bubble overpressure > 5 MPa could have been sufficient to fragment the Curacautín magma. Other mafic explosive eruptions report similar disequilibrium conditions induced by rapid ascent rate, implying that syn-eruptive disequilibrium conditions may control the explosivity of mafic eruptions more generally.

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