Kern, Christoph

Subduction transports volatiles between Earth's mantle, crust, and atmosphere, ultimately creating a habitable Earth. We use isotopes to track carbon from subduction to outgassing along the Aleutian-Alaska Arc. We find substantial along-strike variations in the isotopic composition of volcanic gases, explained by different recycling efficiencies of subducting carbon to the atmosphere via arc volcanism and modulated by subduction character. Fast and cool subduction facilitates recycling of ~43 to 61% sediment-derived organic carbon to the atmosphere through degassing of central Aleutian volcanoes, while slow and warm subduction favors forearc sediment removal, leading to recycling of ~6 to 9% altered oceanic crust carbon to the atmosphere through degassing of western Aleutian volcanoes. These results indicate that less carbon is returned to the deep mantle than previously thought and that subducting organic carbon is not a reliable atmospheric carbon sink over subduction time scales.

Volcanic plumes are common and far-reaching manifestations of volcanic activity during and be-tween eruptions. Observations of the rate of emission and composition of volcanic plumes are essential to rec-ognize and, in some cases, predict the state of volcanic activity. Measurements of the size and location of theplumes are important to assess the impact of the emission from sporadic or localized events to persistent orwidespread processes of climatic and environmental importance. These observations provide information onvolatile budgets on Earth, chemical evolution of magmas, and atmospheric circulation and dynamics. Space-based observations during the last decades have given us a global view of Earth’s volcanic emission, particularlyof sulfur dioxide (SO2). Although none of the satellite missions were intended to be used for measurementof volcanic gas emission, specially adapted algorithms have produced time-averaged global emission budgets.These have confirmed that tropospheric plumes, produced from persistent degassing of weak sources, dominatethe total emission of volcanic SO2. Although space-based observations have provided this global insight intosome aspects of Earth’s volcanism, it still has important limitations. The magnitude and short-term variabilityof lower-atmosphere emissions, historically less accessible from space, remain largely uncertain. Operationalmonitoring of volcanic plumes, at scales relevant for adequate surveillance, has been facilitated through the useof ground-based scanning differential optical absorption spectrometer (ScanDOAS) instruments since the be-ginning of this century, largely due to the coordinated effort of the Network for Observation of Volcanic andAtmospheric Change (NOVAC). In this study, we present a compilation of results of homogenized post-analysisof measurements of SO2flux and plume parameters obtained during the period March 2005 to January 2017of 32 volcanoes in NOVAC. This inventory opens a window into the short-term emission patterns of a diverseset of volcanoes in terms of magma composition, geographical location, magnitude of emission, and style oferuptive activity. We find that passive volcanic degassing is by no means a stationary process in time and thatlarge sub-daily variability is observed in the flux of volcanic gases, which has implications for emission budgetsproduced using short-term, sporadic observations. The use of a standard evaluation method allows for intercom-parison between different volcanoes and between ground- and space-based measurements of the same volcanoes.The emission of several weakly degassing volcanoes, undetected by satellites, is presented for the first time. Wealso compare our results with those reported in the literature, providing ranges of variability in emission notaccessible in the past. The open-access data repository introduced in this article will enable further exploitationof this unique dataset, with a focus on volcanological research, risk assessment, satellite-sensor validation, andimproved quantification of the prevalent tropospheric component of global volcanic emission.

This work presents a new database of SO2 and CO2 fluxes from the Southern Central American Volcanic Arc (SCAVA) for the period 2015–2016. We report 300 SO2 flux measurements from 10 volcanoes and gas ratios from 11 volcanoes in Costa Rica and Nicaragua representing the most extensive available assessment of this 500 km arc segment. The SO2 flux from SCAVA is estimated at 6,24061,150 T/d, about a factor of three higher than previous estimations (1972–2013). We attribute this increase in part to our more complete assessment of the arc. Another consideration in interpreting the difference is the context of increased volcanic activity, as there were more eruptions in 2015–2016 than in any period since 1980. A potential explanation for increased degassing and volcanic activity is a change in crustal stress regime (from compression to extension, opening volcanic conduits) following two large (Mw>7) earthquakes in the region in 2012. The CO2 flux from the arc is estimated at 22,50064,900 T/d, which is equal to or greater than estimates of C input into the SCAVA subduction zone. Time-series data sets for arc degassing need to be improved in temporal and spatial coverage to robustly constrain volatile budgets and tectonic controls. Arc volatile budgets are strongly influenced by short-lived degassing events and arc systems likely display significant short-term variations in volatile output, calling for expansion of nascent geochemical monitoring networks to achieve spatial and temporal coverage similar to traditional geophysical networks.

Volcanic eruptions involving interaction with water are amongst the most violent and unpredictable geologic phenomena on Earth. Phreatic eruptions are exceptionally difficult to forecast by traditional geophysical techniques. Here we report on short-term precursory variations in gas emissions related to phreatic blasts at Poás volcano, Costa Rica, as measured with an in situ multiple gas analyzer that was deployed at the edge of the erupting lake. Gas emitted from this hyper-acid crater lake approaches magmatic values of SO2/CO2 1–6 days prior to eruption. The SO2 flux derived from magmatic degassing through the lake is measureable by differential optical absorption spectrometry (sporadic campaign measurements), which allows us to constrain lake gas output and input for the major gas species during eruptive and non-eruptive periods. We can further calculate power supply to the hydrothermal system using volatile mass balance and thermodynamics, which indicates that the magmatic heat flux into the shallow hydrothermal system increases from ∼27 MW during quiescence to ∼59 MW during periods of phreatic events. These transient pulses of gas and heat from the deeper magmatic system generate both phreatic eruptions and the observed short-term changes in gas composition, because at high gas flux scrubbing of sulfur by the hydrothermal system is both kinetically and thermodynamically inhibited whereas CO2 gas is always essentially inert in hyperacid conditions. Thus, the SO2/CO2 of lake emissions approaches magmatic values as gas and power supply to the sub-limnic hydrothermal system increase, vaporizing fluids and priming the hydrothermal system for eruption. Our results suggest that highfrequency real-time gas monitoring could provide useful short-term eruptive precursors at volcanoes prone to phreatic explosions

Active long-path differential optical absorption spectroscopy (LP-DOAS) has been an effective tool for measuring atmospheric trace gases for several decades. However, instruments were large, heavy and powerinefficient, making their application to remote environments extremely challenging. Recent developments in fibre-coupling telescope technology and the availability of ultraviolet light emitting diodes (UV-LEDS) have now allowed us to design and construct a lightweight, portable, low-power LP-DOAS instrument for use at remote locations and specifically for measuring degassing from active volcanic systems. The LP-DOAS was used to measure sulfur dioxide (SO2) emissions from La Fossa crater, Vulcano, Italy, where column densities of up to 1.2 1018 molec cm􀀀2 ( 500 ppmm) were detected along open paths of up to 400m in total length. The instrument’s SO2 detection limit was determined to be 2 1016 molec cm􀀀2 ( 8 ppmm), thereby making quantitative detection of even trace amounts of SO2 possible. The instrument is capable of measuring other volcanic volatile species as well. Though the spectral evaluation of the recorded data showed that chlorine monoxide (ClO) and carbon disulfide (CS2/ were both below the instrument’s detection limits during the experiment, the upper limits for the X/ SO2 ratio (XDClO, CS2/ could be derived, and yielded 2 10􀀀3 and 0.1, respectively. The robust design and versatility of the instrument make it a promising tool for monitoring of volcanic degassing and understanding processes in a range of volcanic systems.

Volcanoes are very strong sources of sulphur, acids and other gases, as well as particles, that are of atmospheric relevance. Some gases only behave as passive tracers, others affect the formation, growth or chemical characteristics of aerosol particles and many lead to adverse effects on vegetation and human health when deposited in the vicinity of volcanoes. In this article the main effects of volcanic emissions on atmospheric chemistry are discussed, with a focus on sulphur and halogen compounds, and to a smaller extent on climate. We primarily focus on quiescent degassing but the main effects of explosive eruptions on the troposphere and stratosphere are covered as well. The key distinction between chemistry in magmatic and hydrothermal settings and the atmosphere is that the atmosphere is oxidising whereas the chemistry is typically reducing in the former cases due to very low oxygen concentrations. Rapid catalytic cycles involving radicals are a further characteristic of atmospheric chemistry. Most reaction cycles involve the photolysis of molecules as a key part of the reaction chains. Recent measurements of halogen radicals in volcanic plumes showed that volcanic plumes are chemically very active. We explain the formation mechanism of halogen oxides in plumes as well as their relevance for the atmosphere.