Tunable diode laser measurements of hydrothermal/volcanic CO2 and implications for the global CO2 budget

Quantifying the CO2 flux sustained by low-temperature fumarolic fields in hydrothermal/volcanic environments has remained a challenge, to date. Here, we explored the potential of a commercial infrared tunable laser unit for quantifying such fumarolic volcanic/hydrothermal CO2 fluxes. Our field tests were conducted between April 2013 and March 2014 at Nea Kameni (Santorini, Greece), Hekla and Krýsuvík (Iceland) and Vulcano (Aeolian Islands, Italy). At these sites, the tunable laser was used to measure the path-integrated CO2 mixing ratios along cross sections of the fumaroles' atmospheric plumes. By using a tomographic post-processing routine, we then obtained, for each manifestation, the contour maps of CO2 mixing ratios in the plumes and, from their integration, the CO2 fluxes. The calculated CO2 fluxes range from low (5.7 ± 0.9 t d−1; Krýsuvík) to moderate (524 ± 108 t d−1; La Fossa crater, Vulcano). Overall, we suggest that the cumulative CO2 contribution from weakly degassing volcanoes in the hydrothermal stage of activity may be significant at the global scale

Tunable diode laser measurements of hydrothermal/volcanic CO2 and implications for the global CO2 budget

Quantifying the CO2 flux sustained by lowtemperature fumarolic fields in hydrothermal/volcanic environments has remained a challenge, to date. Here, we explored the potential of a commercial infrared tunable laser unit for quantifying such fumarolic volcanic/hydrothermal CO2 fluxes. Our field tests were conducted between April 2013 and March 2014 at Nea Kameni (Santorini, Greece), Hekla and Krýsuvík (Iceland) and Vulcano (Aeolian Islands, Italy). At these sites, the tunable laser was used to measure the path-integrated CO2 mixing ratios along cross sections of the fumaroles’ atmospheric plumes. By using a tomographic post-processing routine, we then obtained, for each manifestation, the contour maps of CO2 mixing ratios in the plumes and, from their integration, the CO2 fluxes. The calculated CO2 fluxes range from low (5.7 +/- 0.9 t d-1; Krýsuvík) to moderate (524 +/-108 t d-1; La Fossa crater, Vulcano). Overall, we suggest that the cumulative CO2 contribution from weakly degassing volcanoes in the hydrothermal stage of activity may be significant at the global scale

Crustal structure beneath western and eastern Iceland from surface waves and receiver functions

We determine the crustal structures beneath 14 broad-band seismic stations, deployed in western, eastern, central and southern Iceland, using surface wave dispersion curves and receiver functions. We implement a method to invert receiver functions using constraints obtained from genetic algorithm inversion of surface waves. Our final models satisfy both data sets. The thickness of the upper crust, as defined by the velocity horizon Vs= 3.7 km s−1, is fairly uniform at ∼6.5–9 km beneath the Tertiary intraplate areas of western and eastern Iceland, and unusually thick at 11 km beneath station HOT22 in the far south of Iceland. The depth to the base of the lower crust, as defined by the velocity horizon Vs= 4.1 km s−1 is ∼20–26 km in western Iceland and ∼27–33 km in eastern Iceland. These results agree with those of explosion profiles that detect a thinner crust beneath western Iceland than beneath eastern Iceland. An earlier report of a substantial low-velocity zone beneath the Middle Volcanic Zone in the lower crust is confirmed by a similar observation beneath an additional station there. As was found in previous receiver function studies, the most reliable feature of the results is the clear division into an upper sequence that is a few kilometres thick where velocity gradients are high, and a lower, thicker sequence where velocity gradients are low. The transition to typical mantle velocities is variable, and may range from being very gradational to being relatively sharp and clear. A clear Moho, by any definition, is rarely seen, and there is thus uncertainty in estimates of the thickness of the crust in many areas. Although a great deal of seismic data are now available constraining the structures of the crust and upper mantle beneath Iceland, their geological nature is not well understood

Vernix caseosa as a multi-component defence system based on polypeptides, lipids and their interactions

To access publisher full text version of this article. Please click on the hyperlink in Additional Links fieldVernix caseosa is a white cream-like substance that covers the skin of the foetus and the newborn baby. Recently, we discovered antimicrobial peptides/proteins such as LL-37 in vernix, suggesting host defence functions of vernix. In a proteomic approach, we have continued to characterize proteins in vernix and have identified 20 proteins, plus additional variant forms. The novel proteins identified, considered to be involved in host defence, are cystatin A, UGRP-1, and calgranulin A, B and C. These proteins add protective functions to vernix such as antifungal activity, opsonizing capacity, protease inhibition and parasite inactivation. The composition of the lipids in vernix has also been characterized and among these compounds the free fatty acids were found to exhibit antimicrobial activity. Interestingly, the vernix lipids enhance the antimicrobial activity of LL-37 in vitro, indicating interactions between lipids and antimicrobial peptides in vernix. In conclusion, vernix is a balanced cream of compounds involved in host defence, protecting the foetus and newborn against infection

Gas emissions and crustal deformation from the Krýsuvík high temperature geothermal system, Iceland

The Krýsuvík volcanic system is located on the oblique spreading Reykjanes Peninsula, SW Iceland. Since early 2009 the region has been undergoing episodes of localized ground uplift and subsidence. From April–November 2013, we operated near-real time monitoring of gas emissions in Krýsuvík, using a Multi-component Gas Analyzer System (Multi-GAS), collecting data on gas composition from a fumarole (H₂O, CO₂, SO₂, H₂S). The dataset in this study, comprises a near-continuous gas composition time series, the quantification of diffuse CO₂ gas flux, analytical results for direct samples of dry gas, seismic records, and GPS data. Gas emissions from the Krýsuvík geothermal system were examined and compared with crustal deformation and seismicity. The gas emissions from the Krýsuvík system are H₂O-dominated, with CO₂ as the most abundant dry gas species, followed by smaller concentrations of H₂S. The average subsurface equilibrium temperature was calculated as 278 °C. This is consistent with previous observations made through sporadic spot sampling campaigns. In addition, the semi-continuous Multi-GAS dataset reveals higher variations in gas composition than previously reported by spot sampling. The diffuse soil CO₂ flux is found to be variable between the three studied degassing areas in Krýsuvík, ranging from 10.9–70.9 T/day, with the highest flux in Hveradalir where the Multi-GAS station is located. The total flux is estimated as 101 T/day. Comparison between Multi-GAS and geophysical data shows that peaks of H₂O-rich emissions appears to follow crustal movements. Coinciding with the H₂O-rich peaks, SO₂ is detected in minor amounts (~0.6 ppmv), allowing for calculations of H₂O/SO₂, CO₂/SO₂ and H₂S/SO₂ ratios. This is the first time SO₂ has been detected in the Krýsuvík area. The large variations in H₂O/CO₂ and H₂O/H₂S ratios are considered to reflect variable degassing activity in the fumarole. The activity of the fumarole appears less intense during intervals of low or no recorded seismic events. The H2₂O/CO₂ and H₂O/H₂S ratios are lower, presumably due to H₂O condensation affecting the steam jet before reaching the Multi-GAS inlet tube

Insights into volcanic hazards and plume chemistry from multi-parameter observations: the eruptions of Fimmvörðuháls and Eyjafjallajökull (2010) and Holuhraun (2014–2015)

The eruptions of Eyjafjallajökull volcano in 2010 (including its initial effusive phase at Fimmvörðuháls and its later explosive phase from the central volcano) and Bárðarbunga volcano in 2014–2015 (at Holuhraun) were widely reported. Here, we report on complementary, interdisciplinary observations made of the eruptive gases and lavas that shed light on the processes and atmospheric impacts of the eruptions, and afford an intercomparison of contrasting eruptive styles and hazards. We find that (i) consistent with other authors, there are substantial differences in the gas composition between the eruptions; namely that the deeper stored Eyjafjallajökull magmas led to greater enrichment in Cl relative to S; (ii) lava field SO2 degassing was measured to be 5–20% of the total emissions during Holuhraun, and the lava emissions were enriched in Cl at both fissure eruptions—particularly Fimmvörðuháls; and (iii) BrO is produced in Icelandic plumes in spite of the low UV levels

Environmental pressure from the 2014–15 eruption of Bárðarbunga volcano, Iceland

The effusive six months long 2014-2015 Bárðarbunga eruption (31 August-27 February) was the largest in Iceland for more than 200 years, producing 1.6 ± 0.3 km3 of lava. The total SO2 emission was 11 ± 5 Mt, more than the amount emitted from Europe in 2011. The ground level concentration of SO2 exceeded the 350 μg m−3 hourly average health limit over much of Iceland for days to weeks. Anomalously high SO2 concentrations were also measured at several locations in Europe in September. The lowest pH of fresh snowmelt at the eruption site was 3.3, and 3.2 in precipitation 105 km away from the source. Elevated dissolved H2SO4, HCl, HF, and metal concentrations were measured in snow and precipitation. Environmental pressures from the eruption and impacts on populated areas were reduced by its remoteness, timing, and the weather. The anticipated primary environmental pressure is on the surface waters, soils, and vegetation of Iceland

New insights into the magmatic-hydrothermal system and volatile budget of Lastarria volcano, Chile: Integrated results from the 2014 IAVCEI CCVG 12th Volcanic Gas Workshop.

Recent geophysical evidence for large-scale regional crustal inflation and localized crustal magma intrusion has made Lastarria volcano (northern Chile) the target of numerous geological, geophysical, and geochemical studies. The chemical composition of volcanic gases sampled during discrete campaigns from Lastarria volcano indicated a well-developed hydrothermal system from direct fumarole samples in A.D. 2006, 2008, and 2009, and shallow magma degassing using measurements from in situ plume sampling techniques in 2012. It is unclear if the differences in measured gas compositions and resulting interpretations were due to artifacts of the different sampling methods employed, short-term excursions from baseline due to localized changes in stress, or a systematic change in Lastarria's magmatic-hydrothermal system between 2009 and 2012. Integrated results from a two-day volcanic gas sampling and measurement campaign during the 2014 International Association of Volcanology and Chemistry of the Earth's Interior (IAVCEI) Commission on the Chemistry of Volcanic Gases (CCVG) 12th Gas Workshop are used here to compare and evaluate current gas sampling and measurement techniques, refine the existing subsurface models for Lastarria volcano, and provide new constraints on its magmatic-hydrothermal system and total degassing budget. While compositional differences among sampling methods are present, distinct compositional changes are observed, which if representative of longterm trends, indicate a change in Lastarria's overall magmatic-hydrothermal system. The composition of volcanic gases measured in 2014 contained high proportions of relatively magma- and water-soluble gases consistent with degassing of shallow magma, and in agreement with the 2012 gas composition. When compared with gas compositions measured in 2006-2009, higher relative H2O/CO2 ratios combined with lower relative CO2/St and H2O/St and stable HCl/St ratios (where St is total S [SO2 + H2S]) are observed in 2012 and 2014. These compositional changes suggest variations in the magmatic-hydrothermal system between 2009 and 2012, with possible scenarios to explain these trends including: (1) decompression-induced degassing due to magma ascent within the shallow crust; (2) crystallization-induced degassing of a stalled magma body; (3) depletion of the hydrothermal system due to heating, changes in local stress, and/or minimal precipitation; and/or (4) acidification of the hydrothermal system. These scenarios are evaluated and compared against the geophysical observations of continuous shallow inflation at ~8 km depth between 1997 and 2016, and near-surface ( < 1 km) inflation between 2000 and 2008, to further refine the existing subsurface models. Higher relative H2O/CO2 observed in 2012 and 2014 is not consistent with the depletion or acidification of a hydrothermal system, while all other observations are consistent with the four proposed models. Based on these observations, we find that scenarios 1 or 2 are the most likely to explain the geochemical and geophysical observations, and propose that targeted shallow interferometric synthetic-aperture radar (InSAR) studies could help discriminate between these two scenarios. Lastly, we use an average SO2 flux of 604 \ub1 296 t/d measured on 22 November 2014, along with the average gas composition and diffuse soil CO2 flux measurements, to estimate a total volatile flux from Lastarria volcano in 2014 of ~12,400 t/d, which is similar to previous estimates from 2012

Ground-Based Measurements of the 2014–2015 Holuhraun Volcanic Cloud (Iceland)

The 2014–2015 Bárðarbunga fissure eruption at Holuhraun in central Iceland was distinguished by the high emission of gases, in total 9.6 Mt SO2, with almost no tephra. This work collates all ground-based measurements of this extraordinary eruption cloud made under particularly challenging conditions: remote location, optically dense cloud with high SO2 column amounts, low UV intensity, frequent clouds and precipitation, an extensive and hot lava field, developing ramparts, and high-latitude winter conditions. Semi-continuous measurements of SO2 flux with three scanning DOAS instruments were augmented by car traverses along the ring-road and along the lava. The ratios of other gases/SO2 were measured by OP-FTIR, MultiGAS, and filter packs. Ratios SO2/HCl = 30–110 and SO2/HF = 30–130 show a halogen-poor eruption cloud. Scientists on-site reported extremely minor tephra production during the eruption. OPC and filter packs showed low particle concentrations similar to non-eruption cloud conditions. Three weather radars detected a droplet-rich eruption cloud. Top of eruption cloud heights of 0.3–5.5 km agl were measured with ground- and aircraft-based visual observations, web camera and NicAIR II infrared images, triangulation of scanning DOAS instruments, and the location of SO2 peaks measured by DOAS traverses. Cloud height and emission rate measurements were critical for initializing gas dispersal simulations for hazard forecasting

Ground-Based measurements of the 2014-2015 holuhraun volcanic cloud (Iceland)

The 2014-2015 Bárðarbunga fissure eruption at Holuhraun in central Iceland was distinguished by the high emission of gases, in total 9.6 Mt SO2, with almost no tephra. This work collates all ground-based measurements of this extraordinary eruption cloud made under particularly challenging conditions: remote location, optically dense cloud with high SO2 column amounts, low UV intensity, frequent clouds and precipitation, an extensive and hot lava field, developing ramparts, and high-latitude winter conditions. Semi-continuous measurements of SO2 flux with three scanning DOAS instruments were augmented by car traverses along the ring-road and along the lava. The ratios of other gases/SO2 were measured by OP-FTIR, MultiGAS, and filter packs. Ratios of SO2/HCl = 30-110 and SO2/HF = 30-130 show a halogen-poor eruption cloud. Scientists on-site reported extremely minor tephra production during the eruption. OPC and filter packs showed low particle concentrations similar to non-eruption cloud conditions. Three weather radars detected a droplet-rich eruption cloud. Top of eruption cloud heights of 0.3-5.5 km agl were measured with ground-and aircraft-based visual observations, web camera and NicAIR II infrared images, triangulation of scanning DOAS instruments, and the location of SO2 peaks measured by DOAS traverses. Cloud height and emission rate measurements were critical for initializing gas dispersal simulations for hazard forecasting