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R.B. Symonds

Publications and source records attributed to R.B. Symonds.

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Magmatic gas scrubbing: Implications for volcano monitoring

Despite the abundance of SO2(g) in magmatic gases, precursory increases in magmatic SO2(g) are not always observed prior to volcanic eruption, probably because many terrestrial volcanoes contain abundant groundwater or surface water that scrubs magmatic gases until a dry pathway to the atmosphere is established. To better understand scrubbing and its implications for volcano monitoring, we model thermochemically the reaction of magmatic gases with water. First, we inject a 915??C magmatic gas from Merapi volcano into 25??C air-saturated water (ASW) over a wide range of gas/water mass ratios from 0.0002 to 100 and at a total pressure of 0.1 MPa. Then we model closed-system cooling of the magmatic gas, magmatic gas-ASW mixing at 5.0 MPa, runs with varied temperature and composition of the ASW, a case with a wide range of magmatic-gas compositions, and a reaction of a magmatic gas-ASW mixture with rock. The modeling predicts gas and water compositions, and, in one case, alteration assemblages for a wide range of scrubbing conditions; these results can be compared directly with samples from degassing volcanoes. The modeling suggests that CO2(g) is the main species to monitor when scrubbing exists; another candidate is H2S(g), but it can be affected by reactions with aqueous ferrous iron. In contrast, scrubbing by water will prevent significant SO2(g) and most HCl(g) emissions until dry pathways are established, except for moderate HCl(g) degassing from pH < 0.5 hydrothermal waters. Furthermore, it appears that scrubbing will prevent much, if any, SO2(g) degassing from long-resident boiling hydrothermal systems. Several processes can also decrease or increase H2(g) emissions during scrubbing making H2(g) a poor choice to detect changes in magma degassing. We applied the model results to interpret field observations and emission rate data from four eruptions: (1) Crater Peak on Mount Spurr (1992) where, except for a short post-eruptive period, scrubbing appears to have drastically diminished pre-, inter-, and post-eruptive SO2(g) emissions, but had much less impact on CO2(g) emissions. (2) Mount St. Helens where scrubbing of SO2(g) was important prior to and three weeks after the 18 May 1980 eruption. Scrubbing was also active during a period of unrest in the summer of 1998. (3) Mount Pinatubo where early drying out prevented SO2(g) scrubbing before the climactic 15 June 1991 eruption. (4) The ongoing eruption at Popocate??petl in an arid region of Mexico where there is little evidence of scrubbing. In most eruptive cycles, the impact of scrubbing will be greater during pre- and post-eruptive periods than during the main eruptive and intense passive degassing stages. Therefore, we recommend monitoring the following gases: CO2(g) and H2S(g) in precursory stages; CO2(g), H2S(g), SO2(g), HCl(g), and HF(g) in eruptive and intense passive degassing stages; and CO2(g) and H2S(g) again in the declining stages. CO2(g) is clearly the main candidate for early emission rate monitoring, although significant early increases in the intensity and geographic distribution of H2S(g) emissions should be taken as an important sign of volcanic unrest and a potential precursor. Owing to the difficulty of extracting SO2(g) from hydrothermal waters, the emergence of > 100 t/d (tons per day) of SO2(g) in addition to CO2(g) and H2S(g) should be taken as a criterion of magma intrusion. Finally, the modeling suggests that the interpretation of gas-ratio data requires a case-by-case evaluation since ratio changes can often be produced by several mechanisms; nevertheless, several gas ratios may provide useful indices for monitoring the drying out of gas pathways. Published by Elsevier Science B.V.

Journal of Volcanology and Geothermal Research↗

Long-term geochemical surveillance of fumaroles at Showa-Shinzan dome, Usu volcano, Japan

This study investigates 31 years of fumarole gas and condensate (trace elements) data from Showa-Shinzan, a dacitic dome-cryptodome complex that formed during the 1943-1945 eruption of Usu volcano. Forty-two gas samples were collected from the highest-temperature fumarole, named A-1, from 1954 (800??C) to 1985 (336??C), and from lower-temperature vents. Condensates were collected contemporaneously with the gas samples, and we reanalyzed ten of these samples, mostly from the A-1 vent, for 32 cations and three anions. Modeling using the thermochemical equilibrium program, SOLVGAS, shows that the gas samples are mild disequilibrium mixtures because they: (a) contain unequilibrated sedimentary CH4 and NH3; (b) have unequilibrated meteoric water; or (c) lost CO, either by air oxidation or by absorption by the sodium hydroxide sampling solution. SOLVGAS also enabled us to restore the samples by removing these disequilibrium effects, and to estimate their equilibrium oxygen fugacities and amounts of S2 and CH4. The restored compositions contain > 98% H2O with minor to trace amounts of CO2, H2, HCl, SO2, HF, H2S, CO, S2 and CH4. We used the restored gas and condensate data to test the hypotheses that these time-series compositional data from the dome's fumaroles provide: (1) sufficient major-gas data to analyze long-term degassing trends of the dome's magma-hydrothermal system without the influence of sampling or contamination effects; (2) independent oxygen fugacity-versus-temperature estimates of the Showa-Shinzan dacite; (3) the order of release of trace elements, especially metals, from magma; and (4) useful information for assessing volcanic hazards. The 1954-1985 restored A-1 gas compositions confirm the first hypothesis because they are sufficient to reveal three long-term degassing trends: (1) they became increasingly H2O-rich with time due to the progressive influx of meteoric water into the dome; (2) their C/S and S/Cl ratios decreased dramatically while their Cl/F ratios stayed roughly constant, indicating the progressive outgassing of less soluble components (F ??? Cl > S > C) from the magma reservoir; and (3) their H2O/H2, CO2/CO and H2S/SO2 ratios increased significantly in concert with equilibrium changes expected for the ??? 500??C temperature drop. When plotted against reciprocal temperature, the restored-gas log oxygen fugacities follow a tight linear trend from < NNO + 0.5 at > 800??C to NNO + 2.5 at ??? 400??C. This trend largely disproves the second hypothesis because the oxygen fugacities for the < 800??C restored gases can only be explained by mixing of hot magmatic gases with ??? 350??C steam from superheated meteoric water. But above 800??C this trend intersects the opposing linear trend for other Usu eruptive products, implying a log oxygen fugacity of -11.45 at 902??C for the Showa-Shinzan magma. The time-series trace-element data also disprove the third hypothesis because rock- and incrustation-particle contaminants in the condensates account for most of the trace-element variation. Nonetheless, highly volatile elements like B and As are relatively unaffected by this particle contamination, and they show similar time-series trends as Cl and F. Finally, except for infrequent sampling around the 1977 Usu eruption, the results generally confirm the fourth hypothesis, since the time-series trends for the major gases and selected trace elements indicate that, with time, the system cooled, degassed and was infiltrated by meteoric water, all of which are positive signs that volcanic activity declined over the 31-year history. This study also suggests that second boiling of shallow magma within and possibly beneath the cryptodome sustained magmatic degassing for at least 20 years after emplacement.

Journal of Volcanology and Geothermal Research↗

Evaluation of gases, condensates, and SO2 emissions from Augustine volcano, Alaska: the degassing of a Cl-rich volcanic system

After the March-April 1986 explosive eruption a comprehensive gas study at Augustine was undertaken in the summers of 1986 and 1987. Airborne COSPEC measurements indicate that passive SO2 emission rates declined exponentially during this period from 380??45 metric tons/day (T/D) on 7/24/86 to 27??6 T/D on 8/24/87. These data are consistent with the hypothesis that the Augustine magma reservoir has become more degassed as volcanic activity decreased after the spring 1986 eruption. Gas samples collected in 1987 from an 870??C fumarole on the andesitic lava dome show various degrees of disequilibrium due to oxidation of reduced gas species and condensation (and loss) of H2O in the intake tube of the sampling apparatus. Thermochemical restoration of the data permits removal of these effects to infer an equilibrium composition of the gases. Although not conclusive, this restoration is consistent with the idea that the gases were in equilibrium at 870??C with an oxygen fugacity near the Ni-NiO buffer. These restored gas compositions show that, relative to other convergent plate volcanoes, the Augustine gases are very HCl rich (5.3-6.0 mol% HCl), S rich (7.1 mol% total S), and H2O poor (83.9-84.8 mol% H2O). Values of ??D and ??18O suggest that the H2O in the dome gases is a mixture of primary magmatic water (PMW) and local seawater. Part of the Cl in the Augustine volcanic gases probably comes from this shallow seawater source. Additional Cl may come from subducted oceanic crust because data by Johnston (1978) show that Cl-rich glass inclusions in olivine crystals contain hornblende, which is evidence for a deep source (>25km) for part of the Cl. Gas samples collected in 1986 from 390??-642??C fumaroles on a ramp surrounding the inner summit crater have been oxidized so severely that restoration to an equilibrium composition is not possible. H and O isotope data suggest that these gases are variable mixtures of seawater, FMW, and meteoric steam. These samples are much more H2O-rich (92%-97% H2O) than the dome gases, possibly due to a larger meteoric steam component. The 1986 samples also have higher Cl/S, S/C, and F/Cl ratios, which imply that the magmatic component in these gases is from the more degassed 1976 magma. Thus, the 1987 samples from the lava dome are better indicators than the 1986 samples of degassing within the Augustine magma reservoir, even though they were collected a year later and contain a significant seawater component. Future gas studies at Augustine should emphasize fumaroles on active lava domes. Condensates collected from the same lava-dome fumarole have enrichments ot 107-102 in Cl, Br, F, B, Cd, As, S, Bi, Pb, Sb, Mo, Zn, Cu, K, Li, Na, Si, and Ni. Lower-temperature (200??-650??C) fumaroles around the volcano are generally less enriched in highly volatile elements. However, these lower-termperature fumaroles have higher concentration of rock-forming elements, probably derived from the wall rock. ?? 1990 Springer-Verlag.

Bulletin of Volcanology↗

Volatilization, transport and sublimation of metallic and non-metallic elements in high temperature gases at Merapi Volcano, Indonesia

Condensates, silica tube sublimates and incrustations were sampled from 500–800°C fumaroles and lava samples were collected at Merapi Volcano, Indonesia in Jan.–Feb., 1984. With respect to the magma, Merapi gases are enriched by factors greater than 10 5 in Se, Re, Bi and Cd; 10 4 –10 5 in Au, Br, In, Pb and W; 10 3 –10 4 in Mo, Cl, Cs, S, Sn and Ag; 10 2 –10 3 in As, Zn, F and Rb; and 1–10 2 in Cu, K, Na, Sb, Ni, Ga, V, Fe, Mn and Li. The fumaroles are transporting more than 10 6 grams/day ( g d "> gd ) of S, Cl and F; 10 4 –10 6 g/d of Al, Br, Zn, Fe, K and Mg; 10 3 –10 4 g d "> gd of Pb, As, Mo, Mn, V, W and Sr; and less than 10 3 g d "> gd of Ni, Cu, Cr, Ga, Sb, Bi, Cd, Li, Co and U. With decreasing temperature (800-500°C) there were five sublimate zones found in silica tubes: 1) cristobalite and magnetite (first deposition of Si, Fe and Al); 2) K-Ca sulfate, acmite, halite, sylvite and pyrite (maximum deposition of Cl, Na, K, Si, S, Fe, Mo, Br, Al, Rb, Cs, Mn, W, P, Ca, Re, Ag, Au and Co); 3) aphthitalite (K-Na sulfate), sphalerite, galena and Cs-K. sulfate (maximum deposition of Zn, Bi, Cd, Se and In; higher deposition of Pb and Sn); 4) Pb-K chloride and Na-K-Fe sulfate (maximum deposition of Pb, Sn and Cu); and 5) Zn, Cu and K-Pb sulfates (maximum deposition of Pb, Sn, Ti, As and Sb). The incrustations surrounding the fumaroles are also chemically zoned. Bi, Cd, Pb, W, Mo, Zn, Cu, K, Na, V, Fe and Mn are concentrated most in or very close to the vent as expected with cooling, atmospheric contamination and dispersion. The highly volatile elements Br, Cl, As and Sb are transported primarily away from high temperature vents. Ba, Si, P, Al, Ca and Cr are derived from wall rock reactions. Incomplete degassing of shallow magma at 915°C is the origin of most of the elements in the Merapi volcanic gas, although it is partly contaminated by particles or wall rock reactions. The metals are transported predominantly as chloride species. As the gas cools in the fumarolic environment, it becomes saturated with sublimate phases that fractionate from the gas in the order of their equilibrium saturation temperatures. Devolatilization of a cooling batholith could transport enough acids and metals to a hydrothermal system to play a significant role in forming an ore deposit. However, sublimation from a high temperature, high velocity carrier gas is not efficient enough to form a large ore deposit. Re, Se, Cd and Bi could be used as supporting evidence for magmatic fluid transport in an ore deposit.

Geochimica et Cosmochimica Acta↗

Dry tilt network at Mount Rainier, Washington

In addition to its primary responsibility of monitoring active Mount St. Helens, the David A. Johnston Cascades Volcano Observatory (CVO) has been charged with obtaining baseline geodetic and geochemical information at each of the other potentially active Cascade volcanoes. Dry tilt and/or trilateration networks were established during 1975-82 at Mount Baker, Mount St. Helens, Mount Hood, Mount Shasta, Lassen Peak, Crater Lake, and Long Valley caldera; coverage was extended during September 1982 to include Mount Rainier.

Open-File Report↗