Thomas J. Casadevall

Chemistry and isotope ratios of sulfur in basalts and volcanic gases at Kilauea volcano, Hawaii

Abstract Eighteen basalts and some volcanic gases from the submarine and subaerial parts of Kilauea volcano were analyzed for the concentration and isotope ratios of sulfur. By means of a newly developed technique, sulfide and sulfate sulfur in the basalts were separately but simultaneously determined. The submarine basalt has 700 ± 100 ppm total sulfur with δ34SΣs of 0.7 ± 0.1 ‰ . The sulfate/sulfide molar ratio ranges from 0.15 to 0.56 and the fractionation factor between sulfate and sulfide is +7.5 ± 1.5‰ . On the other hand, the concentration and δ34SΣs values of the total sulfur in the subaerial basalt are reduced to 150 ± 50 ppm and −0.8 ± 0.2‰ , respectively. The sulfate to sulfide ratio and the fractionation factor between them are also smaller, 0.01 to 0.25 and +3.0‰, respectively. Chemical and isotopic evidence strongly suggests that sulfate and sulfide in the submarine basalt are in chemical and isotopic equilibria with each other at magmatic conditions. Their relative abundance and the isotope fractionation factors may be used to estimate the ƒo 2 and temperature of these basalts at the time of their extrusion onto the sea floor. The observed change in sulfur chemistry and isotopic ratios from the submarine to subaerial basalts can be interpreted as degassing of the SO2 from basalt thereby depleting sulfate and 34S in basalt. The volcanic sulfur gases, predominantly SO2, from the 1971 and 1974 fissures in Kilauea Crater have δ34S values of 0.8 to 0.9%., slightly heavier than the total sulfur in the submarine basalts and definitely heavier than the subaerial basalts, in accord with the above model. However, the δ34S value of sulfur gases (largely SO2) from Sulfur Bank is 8.0%., implying a secondary origin of the sulfur. The δ34S values of native sulfur deposits at various sites of Kilauea and Mauna Loa volcanos, sulfate ions of four deep wells and hydrogen sulfide from a geothermal well along the east rift zone are also reported. The high δ34S values (+5 to +6%.o) found for the hydrogen sulfide might be an indication of hot basaltseawater reaction beneath the east rift zone.

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.

Crater lake and post-eruption hydrothermal activity, El Chichón Volcano, Mexico

Abstract Explosive eruptions of Volcan El Chichon in Chiapas, Mexico on March 28 and April 3–4, 1982 removed 0.2 km3 of rock to form a 1-km-wide 300-m-deep summit crater. By late April 1982 a lake had begun to form on the crater floor, and by November 1982 it attained a maximum surface area of 1.4 × 105 m2 and a volume of 5 × 106 m3. Accumulation of 4–5 m of rainfall between July and October 1982 largely formed the lake. In January 1983, temperatures of fumaroles on the crater floor and lower crater walls ranged from 98 to 115°C; by October 1983 the maximum temperature of fumarole emissions was 99°C. In January 1983 fumarole gas emissions were greater than 99 vol. % H2O with traces of CO2, SO2, and H2S. The water of the lake was a hot (T = 52–58°C), acidic (pH = 0.5), dilute solution (34,046 mg L−1 dissolved solids; Cl/S = 20.5). Sediment from the lake contains the same silicate minerals as the rocks of the 1982 pyroclastic deposits, together with less than 1% of elemental sulfur. The composition and temperature of the lake water is attributed to: (1) solution of fumarole emissions; (2) reaction of lake water with hot rocks beneath the lake level; (3) sediments washed into the lake from the crater walls; (4) hydrothermal fluids leaching sediments and formational waters in sedimentary rocks of the basement; (5) evaporation; and (6) precipitation.

Emission rates of sulfur dioxide and carbon dioxide from Redoubt Volcano, Alaska during the 1989–1990 eruptions

Airborne measurements of sulfur dioxide emission rates in the gas plume emitted from fumaroles in the summit crater of Redoubt Volcano were started on March 20, 1990 using the COSPEC method. During the latter half of the period of intermittent dome growth and destruction, between March 20 and mid-June 1990, sulfur dioxide emission rates ranged from approximately 1250 to 5850 t/d, rates notably higher than for other convergent-plate boundary volcanoes during periods of active dome growth. Emission rates following the end of dome growth from late June 1990 through May 1991 decreased steadily to less than 75 t/d. The largest mass of sulfur dioxide was released during the period of explosive vent clearing when explosive degassing on December 14–15 injected at least 175,000 ± 50,000 tonnes of SO2 into the atmosphere. Following the explosive eruptions of December 1989, Redoubt Volcano entered a period of intermittent dome growth from late December 1989 to mid-June 1990 during which Redoubt emitted a total mass of SO2 ranging from 572,000 ± 90,000 tonnes to 680,000 ± 90,000 tonnes. From mid-June 1990 through May 1991, the volcano was in a state of posteruption degassing into the troposphere, producing approximately 183,000 ± 50,000 tonnes of SO2. We estimate that Redoubt Volcano released a minimum mass of sulfur dioxide of approximately 930,000 tonnes. While COSPEC data were not obtained frequently enough to enable their use in eruption prediction, SO2 emission rates clearly indicated a consistent decline in emission rates between March through October 1990 and a continued low level of emission rates through the first half of 1991. Values from consecutive daily measurements of sulfur dioxide emission rates spanning the March 23, 1990 eruption decreased in the three days prior to eruption. That decrease was coincident with a several-fold increase in the frequency of shallow seismic events, suggesting partial sealing of the magma conduit to gas loss that resulted in pressurization of the shallow magma system and an increase in earthquake activity. Unlike the short-term SO2 decrease in March 1990, the long-term decrease of sulfur dioxide emission rates from March 1990 through May 1991 was coincident with low rates of seismic energy release and was interpreted to reflect gradual depressurization of the shallow magma reservoir. The long-term declines in seismic energy release and in SO2 emission rates led AVO scientists to conclude on April 19, 1991 that the potential for further eruptive activity from Redoubt Volcano had diminished, and on this basis, the level of concern color code for the volcano was changed from code yellow (Volcano is restless; earthquake activity is elevated; activity may include extrusion of lava) to code green (Volcano is in its normal ‘dormant’ state).

The Uwekahuna Ash Member of the Puna Basalt: product of violent phreatomagmatic eruptions at Kilauea volcano, Hawaii, between 2800 and 210014C years ago

Abstract Kilauea volcanos reputation for relatively gentle effusive eruptions belies a violent geologic past, including several large phreatic and phreatomagmatic eruptions that are recorded by Holocene pyroclastic deposits which mantle Kilaueas summit area and the southeast flank of adjacent Mauna Loa volcano. The most widespread of these deposits whose original distribution can be reconstructed is the Uwekahuna Ash Member of the Puna Basalt, a basaltic surge and fall deposit emplaced during two or more eruptive episodes separated by a few decades to several centuries. The first episode occurred between 2770 ± 70 and 2265 ± 50 14 C yr ago. It included two major pyroclastic surges, each preceded by unusually vigorous lava fountaining from a vent near the volcanos summit. Before the second eruptive episode, 2110 ± 120 14 C yr ago, plants had re-colonized the rainforest environment northeast of the summit, and at least two lava flows from Mauna Loa had buried parts of the first-episode deposits. The second episode also began with vigorous lava fountaining, followed by widespread lithic ashfall, a third major surge and finally a fourth fountaining event. Before the final pumice deposit could be significantly reworked, it was partly buried by picritic basalt flows that are unusual in Kilaueas summit area. In proximal areas, the Uwekahuna Ash Member is more than 1 m thick (locally > 5 m) and includes lithic blocks up to 0.8 m in diameter. Coarse, primarily lithic debris was deposited around the vent by laterally expanding surges; fallout deposits accumulated preferentially to the northeast under the influence of high-altitude counter-tradewinds. The area devastated by surges and originally buried by at least 15 cm of the Uwekahuna was about 420 km 2 . The bulk volume of the deposits was approximately 0.3 km 3 , including less than 0.1 km 3 of juvenile material. Juvenile constituents are olivine-tholeiitic basalts similar in major-element composition to typical Kilauea summit lava flows, but variations in both major elements and trace elements suggest that the eruptions tapped more than a single, uniform source region. We infer that the eruptions which produced the Uwekahuna were driven by water interacting with a fluctuating magma column. Magma withdrawal episodes may have been accompanied by large-volume submarine effusive eruptions and by summit collapse. The volume, extent and character of the Uwekahuna deposits underscore the hazards posed by relatively infrequent but potentially devastating explosive eruptions at Kilauea, as well as at other basaltic volcanoes.

Evaluation of gas data from high-temperature fumaroles at Mount St. Helens, 1980–1982☆

Abstract The Mount St. Helens fumarole gases show linear composition trends during periods of noneruptive degassing between September 1980 and October 1981. The trends are characterized by increasing H2O and decreasing CO2 and sulfur. Maximum fumarole temperatures also show a linear decrease during this period. High-temperature fumarole gases collected from the crater and dome between September 1980 and July 1982 are all H2O-rich (> 90%) with 1–10% CO2 and small amounts of H2S, SO2, H2, CO, HC, and HF. Trace amounts of COS and S2 are present, and occasional observations of minor CH4 appear to result from contamination or low-temperature reactions in sample vessels. The O2 fugacities of the gases remain near Ni-NiO during cooling. The low sulfur content of the gases obviates the need for extensive gas-rock oxygen exchange to maintain fO2s near Ni-NiO. A detailed thermodynamic analysis of 50 gas samples collected between September 1980 and December 1981 led to improved compositions for 22 samples. The gases were initially in a state of equilibrium, but disequilibrium modifications from atmospheric oxidation of H2 and, to a lesser extent, CO occurred within the upper portions of the fumarole vents. The last temperatures of equilibrium for the fumarole gases range from 800°C to 650°C and are nearly always higher than the collection temperatures. No evidence was found of disequilibrium admixture of surface waters; if such modifications of the fumarole gases occurred, the water must have been added at depth and have reequilibrated with the other gas species at magmatic or near-magmatic temperatures. The highest quality analytical data are obtained by field gas chromatograph measurements and from caustic soda bottle samples. Samples collected in evacuated bottles or by pumping through double stopcock tubes tend to be severely deficient in sulfur due to post-collection reactions between H2S and SO2. It is also necessary to infer the water content of the latter samples.

Evaluation of sulfur dioxide emissions from explosive volcanism: the 1982-1983 eruptions of Galunggung, Java, Indonesia

Abstract Galunggung volcano, Java, awoke from a 63-year quiescence in April 1982, and erupted sporadically through January 1983. During its most violent period from April to October, the Cikasasah Volcano Observatory reported 32 large and 56 moderate to small eruptions. From April 5 through September 19 the Total Ozone Mapping Spectrometer (TOMS), carried on NASAs Nimbus-7 satellite, detected and measured 24 different sulfur dioxide clouds; an estimated 1730 kilotons (kt) of SO2 were outgassed by these explosive eruptions. The trajectories, and rapid dispersion rates, of the SO2 clouds were consistent with injection altitudes below the tropopause. An additional 300 kt of SO2 were estimated to have come from 64 smaller explosive eruptions, based on the detection limit of the TOMS instrument. For the first time, an extended period of volcanic activity was monitored by remote sensing techniques which enabled observations of both the entire SO2 clouds produced by large explosive eruptions (using TOMS), and the relatively lower levels of SO2 emissions during non-explosive outgassing (using the Correlation Spectrometer, or COSPEC). Based on COSPEC measurements from August 1982 to January 1983, and on the relationship between explosive and non-explosive degassing, approximately 400 kt of SO2 were emitted during non-explosive activity. The total sulfur dioxide outgassed from Galunggung volcano from April 1982 to January 1983 is calculated to be 2500 kt (± 30%) from both explosive and non-explosive activity. While Galunggung added large quantities of sulfur dioxide to the atmosphere, its sporadic emissions occurred in relatively small events distributed over several months, and reached relatively low altitudes, and are unlikely to have significantly affected aerosol loading of the stratosphere in 1982 by volcanic activity.

Mt. St. Helens: evidence of increased magmatic gas component

Abstract This paper presents measurements of SO 2 flux and ash leachate chemistry from Mt. St. Helens volcano during the period May 18 to July 22 which are in contrast to similar data from before May 18. Comparison of post-18 May SO 2 data with similar data from other volcanoes leads to the conclusion that between 15 and 25 May the SO 2 flux reached typical magmatic levels. Ash leachate chemistry from the eruption of 18 May, 22 June and 22 July also indicate a large magmatic gas component. Concentrations of Cl − and SO 2− 4 on May 18 ash increase with distance from the volcano and decrease with time. Leachate chemistry is used to estimate that a minimum of 2.4 × 10 5 tons of S were released on May 18. Low F concentrations on the ash, though increasing, present to health hazards.

Thermal areas on Kilauea and Mauna Loa Volcanoes, Hawaii

Abstract Active thermal areas are concentrated in three areas on Mauna Loa and three areas on Kilauea. High-temperature fumaroles (115–362° C) on Mauna Loa are restricted to the summit caldera, whereas high-temperature fumaroles on Kilauea are found in the upper East Rift Zone (Mauna Ulu summit fumaroles, 562° C), middle East Rift Zone (1977 eruptive fissure fumaroles), and in the summit caldera. Solfataric activity that has continued for several decades occurs along border faults of Kilauea caldera and at Sulphur Cone on the southwest rift zone of Mauna Loa. Solfataras that are only a few years old occur along recently active eruptive fissures in the summit caldera and along the rift zones of Kilauea. Steam vents and hot-air cracks also occur at the edges of cooling lava ponds, on the summits of lava shields, along faults and graben fractures, and in diffuse patches that may reflect shallow magmatic intrusions.

Recent uplift and hydrothermal activity at Tangkuban Parahu volcano, west Java, Indonesia

Tangkuban Parahu is an active stratovolcano located 17 km north of the city of Bandung in the province west Java, Indonesia. All historical eruptive activity at this volcano has been confined to a complex of explosive summit craters. About a dozen eruptions-mostly phreatic events- and 15 other periods of unrest, indicated by earthquakes or increased thermal activity, have been noted since 1829. The last magmatic eruption occurred in 1910. In late 1983, several small phreatic explosions originated from one of the summit craters. More recently, increased hydrothermal and earthquake activity occurred from late 1985 through 1986. Tilt measurements, using a spirit-level technique, have been made every few months since February 1981 in the summit region and along the south and east flanks of the volcano. Measurements made in the summit region indicated uplift since the start of these measurements through at least 1986. From 1981 to 1983, the average tilt rate at the edges of the summit craters was 40–50 microradians per year. After the 1983 phreatic activity, the tilt rate decreased by about a factor of five. Trilateration surveys across the summit craters and on the east flank of the volcano were conducted in 1983 and 1986. Most line length changes measured during this three-year period did not exceed the expected uncertainty of the technique (4 ppm). The lack of measurable horizontal strain across the summit craters seems to contradict the several years of tilt measurements. Using a point source of dilation in an elastic half-space to model tilt measurements, the pressure center at Tangkuban Parahu is located about 1.5 km beneath the southern part of the summit craters. This is beneath the epicentral area of an earthquake swarm that occurred in late 1983. The average rate in the volume of uplift from 1981 to 1983 was 3 million m3 per year; from 1983 to 1986 it averaged about 0.4 million m3 per year. Possible causes for this uplift are increased pressure within a very shallow magma body or heating and expansion of a confined aquifier.