David L. Finnegan

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

Abstract 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 105 in Se, Re, Bi and Cd; 104–105 in Au, Br, In, Pb and W; 103–104 in Mo, Cl, Cs, S, Sn and Ag; 102–103 in As, Zn, F and Rb; and 1–102 in Cu, K, Na, Sb, Ni, Ga, V, Fe, Mn and Li. The fumaroles are transporting more than 106 grams/day ( g d ) of S, Cl and F; 104–106 g/d of Al, Br, Zn, Fe, K and Mg; 103–104 g d of Pb, As, Mo, Mn, V, W and Sr; and less than 103 g d 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.

Metal emissions from Kilauea, and a suggested revision of the estimated worldwide metal output by quiescent degassing of volcanoes

Abstract Measurements of a large suite of metals (Pb, Cd, Cu, Zn and several others) and sulfur at Kilauea volcano over an extended period of time has yielded a detailed record of the atmospheric injection of ordinarily-rare metals from this quiescently degassing volcano, representative of an important type. We have combined the Kilauea data with data of recent studies by others (emissions from volcanoes in the Indonesian arc; the large Laki eruption of two centuries ago; Etna; estimates of total volcanic emissions of sulfur) to form the basis for a new working estimate of the rate of worldwide injection of metals to the atmosphere by volcanoes. The new estimate is that volcanoes inject a substantially smaller mass of ordinarily-rare metals into the atmosphere than was stated in a widely cited previous estimate [J.O. Nriagu, A global assessment of natural sources of atmospheric trace metals, Nature 338 (1989) 47–49]. Our estimate, which is an upper limit, is an annual injection mass of about 10,000 tons of the metals considered, versus the earlier estimate of about 23,000 tons. Also, the proportions of the metals are substantially different in our new estimate.

Vapor saturation and accumulation in magmas of the 1989–1990 eruption of Redoubt Volcano, Alaska

Abstract The 1989–1990 eruption of Redoubt Volcano, Alaska, provided an opportunity to compare petrologic estimates of SO 2 and Cl emissions with estimates of SO 2 emissions based on remote sensing data and estimates of Cl emissions based on plume sampling. In this study, we measure the sulfur and chlorine contents of melt inclusions and matrix glasses in the eruption products to determine petrologic estimates of SO 2 and Cl emissions. We compare the results with emission estimates based on COSPEC and TOMS data for SO 2 and data for Cl/SO 2 in plume samples. For the explosive vent clearing period (December 14–22, 1989), the petrologic estimate for SO 2 emission is 21,000 tons, or ~12% of a TOMS estimate of 175,000 tons. For the dome growth period (December 22, 1989 to mid-June 1990), the petrologic estimate for SO 2 emission is 18,000 tons, or ~3% of COSPEC-based estimates of 572,000–680,000 tons. The petrologic estimates give a total SO 2 emission of only 39,000 tons compared to an integrated TOMS/COSPEC emission estimate of ~1,000,000 tons for the whole eruption, including quiescent degassing after mid-June 1990. Petrologic estimates also appear to underestimate Cl emissions, but apparent HCl scavenging in the plume complicates Cl emission comparisons. Several potential sources of ‘excess sulfur’ often invoked to explain petrologic SO 2 deficits are concluded to be unlikely for the 1989–1990 Redoubt eruption — e.g., breakdown of sulfides, breakdown of anhydrite, release of SO 2 from a hydrothermal system, degassing of commingled infusions of basalt in the magma chamber, and syn-eruptive degassing of sulfur from melt present in non-erupted magma. Leakage and/or diffusion of sulfur from melt inclusions do not provide convincing explanations for the petrologic SO 2 deficits either. The main cause of low petrologic estimates for SO 2 is that melt inclusions do not represent the total sulfur content of the Redoubt magmas, which were vapor-saturated magmas carrying most of their sulfur in an accumulated vapor phase. Almost all the sulfur of the SO 2 emissions was present prior to emission as accumulated magmatic vapor at 6–10 km depth in the magma that supplied the eruption; whole-rock normalized concentrations of gaseous excess S in these magmas remained at ~0.2 wt.% throughout the eruption, equivalent to ~0.7 vol.% at depth. Data for CO 2 emissions during the eruption indicate that CO 2 at whole-rock concentrations of ~0.6 wt.% in the erupted magma was a key factor in creating the vapor saturation and accumulation condition making a vapor phase source of excess sulfur possible at depth. When explosive volcanism involves magma with accumulated vapor, melt inclusions do not provide a sufficient basis for predicting SO 2 emissions. Thus, petrologic estimates made for SO 2 emissions during explosive eruptions of the past may be too low and may significantly underestimate impacts on climate and the chemistry of the atmosphere.

The use of7LiOH-impregnated filters for the collection of acidic gases and analysis by instrumental neutron activation analysis

A simple system was designed using7LiOH-impregnated filters to collect acidic gases from ambient air and from highly concentrated volcanic plumes or gas streams. These filters were developed for analysis using instrumental neutron activation analysis, but other analytical techniques could be used as well. The sampling system was designed to use a series of 1–3 M7LiOH-impregnated filters to collect high concentrations of acidic gases found in gas plumes of active volcanoes. The filters are quantitative for SO2 and the halide acids when sufficient base is present to neutralize the acidic species. Extremely high concentrations of SO2 may not be collected quantitatively since SO2 is a relatively weak Lewis acid compared to the halide acids. The acidic oxides of Sb, As, and Se were also collected quantitatively. A particle filter preceded the impregnated filters in order to remove particles from the fumes. This system has proven effective under difficult sampling conditions and, since it is portable and light weight, it could be used for many volcanological applications where high levels of acidic gaseous phase species need to be collected.

Chlorine, fluorine, and sulfur emissions from Mount Erebus, Antarctica and estimated contributions to the Antarctic atmosphere

The discharge rates of halogens in aerosols and gases emitted from Mount Erebus between December 1986 and January 1991 were estimated by combining element-to-sulfur ratios on filter samples with SO2 output measured by COSPEC. The halogen and sulfur content of the gas vary in a quasi-cyclical pattern possibly because of a heterogeneous distribution of volatiles in the Erebus magmatic system. The emission rates of HF and HCl have increased twofold since 1986 reaching 6 and 13.3 Gg yr−1, respectively, in 1991, making Erebus an important contributor of halogens to the Antarctic atmosphere.

Osmium isotopes in the aerosols of the mantle volcano Mauna Loa

Aerosols and reactive gases from the spring 1984 eruption of Mauna Loa Volcano on Hawaii were collected and analyzed for osmium and its isotopic composition. The measured187Os/186Os ratio of1.14 ± 0.03 is close to the ratio in matter with solar systemRe/Os abundance. This result shows that the aerosols from Mauna Loa originated in the mantle and that their composition was not or only slightly influenced by their contact with the crust.