While explosive volcanic eruptions cause ozone loss in the current atmosphere due to an enhancement in the availability of reactive chlorine following the stratospheric injection of sulfur, future eruptions are expected to increase total column ozone as halogen loading approaches preindustrial levels. The timing of this shift in the impact of major volcanic eruptions on the thickness of the ozone layer is poorly known. Modeling four possible climate futures, we show that scenarios with the smallest increase in greenhouse gas concentrations lead to the greatest risk to ozone from heterogeneous chemical processing following future eruptions. We also show that the presence in the stratosphere of bromine from natural, very short-lived biogenic compounds is critically important for determining whether future eruptions will lead to ozone depletion. If volcanic eruptions inject hydrogen halides into the stratosphere, an effect not considered in current ozone assessments, potentially profound reductions in column ozone would result.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1002/2017GL073972

Ozone depletion following future volcanic eruptions

Abstract Volcanic eruptions have long been studied for their wide range of climatic effects. Although global-scale climatic impacts following the formation of stratospheric sulfate aerosol are well understood, many aspects of the evolution of the early volcanic aerosol cloud and regional impacts are uncertain. In the last twenty years, several advances have been made, mainly due to improved satellite measurements and observations enabling the effects of small-magnitude eruptions to be quantified, new proxy reconstructions used to investigate the impact of past eruptions, and state-of-the-art aerosol-climate modelling that has led to new insights on how volcanic eruptions affect the climate. Looking to the future, knowledge gaps include the role of co-emissions in volcanic plumes, the impact of eruptions on tropical hydroclimate and Northern Hemisphere winter climate, and the role of eruptions in long-term climate change. Future model development, dedicated model intercomparison projects, interdisciplinary collaborations, and the application of advanced statistical techniques will facilitate more complex and detailed studies. Ensuring that the next large-magnitude explosive eruption is well observed will be critical in providing invaluable observations that will bridge remaining gaps in our understanding. 

/pdf/volcanic-effects-on-climate-recent-advances-and-future-2zyl6qwl.pdf

Volcanic effects on climate: recent advances and future avenues

Large explosive tropical volcanic eruptions inject high amounts of gases into the stratosphere, where they disperse globally through the large-scale meridional circulation. There is now increasing observational evidence that volcanic halogens can reach the upper troposphere and lower stratosphere. Here, we present the first study that combines measurement-based data of sulfur, chlorine and bromine releases from tropical volcanic eruptions with complex coupled chemistry climate model simulations taking radiative-dynamical-chemical feedbacks into account. Halogen model input parameters represent a size-time-region-wide average for the Central American eruptions over the last 200 ka ensuring a comprehensive perspective. The simulations reveal global, long-lasting impact on the ozone layer affecting atmospheric composition and circulation for a decade. Column ozone drops below 220 DU (ozone hole conditions) in the tropics, Arctic and Antarctica, increasing biologically active UV by 80 to 400%. Our model results could potentially be validated using high-resolution proxies from ice cores and pollen records.

/pdf/global-ozone-depletion-and-increase-of-uv-radiation-caused-5glgr8bi3i.pdf

Global ozone depletion and increase of UV radiation caused by pre-industrial tropical volcanic eruptions.

Assessment of leachable elements in volcanic ashfall : a review and evaluation of a standardized protocol for ash hazard characterization.

Sulfur partitioning between melt and fluid phase largely controls the environmental impact of volcanic eruptions. Fluid/melt partitioning data also provide the physical basis for interpreting changes in volcanic gas compositions that are used in eruption forecasts. To better constrain some variables that control the behavior of sulfur in felsic systems, in particular the interaction between different volatiles, we studied the partitioning of sulfur between aqueous fluids and haplogranitic melts at 200 MPa and 750–850 °C as a function of oxygen fugacity (Ni–NiO or Re–ReO2 buffer), melt composition (Al/(Na + K) ratio), and fluid composition (NaCl and CO2 content). The data confirm a first-order influence of oxygen fugacity on the partitioning of sulfur. Under “reducing conditions” (Ni–NiO buffer), Dfluid/melt is nearly one order of magnitude larger (323 ± 14 for a metaluminous melt) than under “oxidizing conditions” (Re–ReO2 buffer; 74 ± 5 for a metaluminous melt). This effect is likely related to a major change in sulfur speciation in both melt and fluid. Raman spectra of the quenched fluids show the presence of H2S and HS− under reducing conditions and of SO42− and HSO4− under oxidizing conditions, while SO2 is undetectable. The latter observation suggests that already at the Re–ReO2 buffer, sulfur in the fluid is almost completely in the S6+ state and, therefore, more oxidized than expected according to current models. CO2 in the fluid (up to xCO2 = 0.3) has no effect on the fluid/melt partitioning of sulfur, neither under oxidizing nor under reducing conditions. However, the effect of NaCl depends on redox state. While at oxidizing conditions, Dfluid/melt is independent of xNaCl, the fluid/melt partition coefficient strongly decreases with NaCl content under reducing conditions, probably due to a change from H2S to NaSH as dominant sulfur species in the fluid. A decrease of Dfluid/melt with alkali content in the melt is observed over the entire compositional range under reducing conditions, while it is prominent only between the peraluminous and metaluminous composition in oxidizing experiments. Overall, the experimental results suggest that for typical oxidized, silicic to intermediate subduction zone magmas, the degassing of sulfur is not influenced by the presence of other volatiles, while under reducing conditions, strong interactions with chlorine are observed. If the sulfur oxidation state is preserved during an explosive eruption, a large fraction of the sulfur released from oxidized magmas may be in the S6+ state and may remain undetected by conventional methods that only measure SO2. Accordingly, the sulfur yield and the possible climatic impact of some eruptions may be severely underestimated.

The partitioning of sulfur between multicomponent aqueous fluids and felsic melts

The adsorption of HCl on volcanic ash

Volcanic degassing provides important information for the assessment of volcanic hazards. Santa Ana and San Miguel are open vent volcanoes along the Central American Volcanic Arc–CAVA, where the magmatism, basaltic to dacitic, is related to the near-orthogonal convergence of the Caribbean Plate and the subducting Cocos Plate. Both volcanoes are the most active ones in El Salvador with recent eruptive events in October 2005 (Santa Ana) and December 2013 (San Miguel), but still not much data on gas composition and emission are available today. At each volcano, SO2 emissions are regularly monitored using ground-based scanning Differential Optical Absorption Spectrometer (Scan-DOAS) instruments that are part of the global “Network for Observation of Volcanic and Atmospheric Change” (NOVAC). We used the data series from these NOVAC stations in order to retrieve SO2 and minimum bromine emissions, which can be retrieved from the same spectral data for the period 2006–2020 at Santa Ana and 2008–2019 at San Miguel. However, BrO was not detected above the detection limit. SO2 emission ranged from 10 to 7,760 t/d, and from 10 to 5,870 t/d for Santa Ana and San Miguel, respectively. In addition, the SO2 emissions are complemented with in situ plume data collected during regular monitoring surveys (2018–2020) and two field campaigns in El Salvador (2019 and 2020). MultiGAS instruments recorded CO2, SO2, H2S and H2 concentrations. We determined an average CO2/SO2 ratio of 2.9 ± 0.6 when peak SO2 concentration exceeded 15 ppmv at Santa Ana, while at San Miguel the CO2/SO2 ratio was 7.4 ± 1.8, but SO2 levels reached only up to 6.1 ppmv. Taking into account these ratios and the SO2 emissions determined in this study, the resulting CO2 emissions are about one order of magnitude higher than those determined so far for the two volcanoes. During the two field campaigns Raschig tubes (active alkaline trap) were used to collect plume samples which were analyzed with IC and ICP-MS to identify and quantify CO2, SO2, HCl, HF, and HBr. Additionally, also 1,3,5-trimethoxybenzene (TMB)-coated denuders were applied and subsequently analyzed by GC-MS to determine the sum of the reactive halogen species (RHS: including Cl2, Br2, interhalogens, hypohalous acids). The RHS to sulfur ratios at Santa Ana and San Miguel lie in the range of 10−5. Although no new insights could be gained regarding changes with volcanic activity, we present the most comprehensive gas geochemical data set of Santa Ana and San Miguel volcanoes, leading to a solid data baseline for future monitoring purposes at both volcanoes and their improved estimate of CO2, SO2 and halogens emissions. Determining the reactive fraction of halogens is a first step towards a better understanding of their effects on the atmosphere.

Geochemical characterization of volcanic gas emissions at Santa Ana and San Miguel volcanoes, El Salvador, using remote-sensing and in situ measurements

Xochilt Gutiérrez

Papers

The adsorption of HCl on volcanic ash

Geochemical characterization of volcanic gas emissions at Santa Ana and San Miguel volcanoes, El Salvador, using remote-sensing and in situ measurements