Geology topics

T.M. Gerlach

Publications and source records attributed to T.M. Gerlach.

At least 19 recordsLinked to original sources

USGS2009

Halogen degassing during ascent and eruption of water-poor basaltic magma

A study of volcanic gas composition and matrix glass volatile concentrations has allowed a model for halogen degassing to be formulated for K??lauea Volcano, Hawai'i. Volcanic gases emitted during 2004-2005 were characterised by a molar SO 2 /HCl of 10-64, with a mean of 33; and a molar HF/HCl of 0-5, with a mean of 1.0 (from approximately 2500 measurements). The HF/HCl ratio was more variable than the SO 2 /HCl ratio, and the two correlate weakly. Variations in ratio took place over rapid timescales (seconds). Matrix glasses of Pele's tears erupted in 2006 have a mean S, Cl and F content of 67, 85 and 173??ppm respectively, but are associated with a large range in S/F. A model is developed that describes the open system degassing of halogens from parental magmas, using the glass data from this study, previously published results and parameterisation of sulphur degassing from previous work. The results illustrate that halogen degassing takes place at pressures of < 1??MPa, equivalent to < ~ 35??m in the conduit. Fluid-melt partition coefficients for Cl and F are low (< 1.5); F only degasses appreciably at < 0.1??MPa above atmospheric pressure, virtually at the top of the magma column. This model reproduces the volcanic gas data and other observations of volcanic activity well and is consistent with other studies of halogen degassing from basaltic magmas. The model suggests that variation in volcanic gas halogen ratios is caused by exsolution and gas-melt separation at low pressures in the conduit. There is no evidence that either diffusive fractionation or near-vent chemical reactions involving halogens is important in the system, although these processes cannot be ruled out. The fluxes of HCl and HF from K??lauea during 2004-5 were ~ 25 and 12??t/d respectively. ?? 2008 Elsevier B.V.

Chemical Geology↗

USGS2008

Summit CO 2 emission rates by the CO 2 /SO 2 ratio method at Kīlauea Volcano, Hawaiʻi, during a period of sustained inflation

The emission rate of carbon dioxide escaping from the summit of Kīlauea Volcano, Hawaiʻi, proved highly variable, averaging 4900 ± 2000 metric tons per day (t/d) in June–July 2003 during a period of summit inflation. These results were obtained by combining over 90 measurements of COSPEC-derived SO 2 emission rates with synchronous CO 2 /SO 2 ratios of the volcanic gas plume along the summit COSPEC traverse. The results are lower than the CO 2 emission rate of 8500 ± 300 t/d measured by the same method in 1995–1999 during a period of long-term summit deflation [Gerlach, T.M., McGee, K.A., Elias, T., Sutton, A.J. and Doukas, M.P., 2002. Carbon dioxide emission rate of Kīlauea Volcano: Implications for primary magma and the summit reservoir. Journal of Geophysical Research-Solid Earth, 107(B9): art. no.-2189.]. Analysis of the data indicates that the emission rates of the present study likely reflect changes in the magma supply rate and residence time in the summit reservoir. It is also likely that emission rates during the inflation period were heavily influenced by SO 2 pulses emitted adjacent to the COSPEC traverse, which biased CO 2 /SO 2 ratios towards low values that may be unrepresentative of the global summit gas plume. We conclude that the SO 2 pulses are consequences of summit re-inflation under way since 2003 and that CO 2 emission rates remain comparable to, but more variable than, those measured prior to re-inflation.

Hawaii↗

USGS2007

Vapor segregation and loss in basaltic melts

Measurements of volcanic gases at Pu'u'O??'o??, Kilauea Volcano, Hawai'i, reveal distinct degassing regimes with respect to vapor segregation and loss during effusive activity in 2004-2005. Three styles of vapor loss are distinguished by the chemical character of the emitted volcanic gases, measured by open path Fourier transform infrared spectroscopy: 1 persistent continuous gas emission, 2 gas piston events, and 3 lava spattering. Persistent continuous gas emission is associated with magma ascent and degassing beneath the crater vents, then eruption of the degassed magma from flank vents. Gas piston events are the result of static gas accumulation at depths of 400-900 m beneath Pu'u'O??'o??. A CO2-rich gas slug travels up the conduit at a few meters per second, displacing magma as it expands. Lava spattering occurs due to dynamic bubble coalescence in a column of relatively stagnant magma. The Large gas bubbles are H2O rich and are generated by open-system degassing at depths of <150 m. Static gas accumulation and dynamic bubble coalescence are both manifestations of vapor segregation in basaltic melts, but their implications differ. Accumulation and segregation of CO2-rich vapor at depth does not deplete the melt of H2O (required to drive lava fountains near to the surface) and therefore gas piston events can occur interspersed with lava fountaining activity. Lava spattering, however, efficiently strips H2O-rich vapor from magma beneath the crater vents; the magma must then erupt effusively from vents on the flank of the cone. ?? 2007 The Geological Society of America.

Geology↗

USGS2006

Puhimau thermal area: a window into the upper east rift zone of Kilauea Volcano, Hawaii?

We report the results of two soil CO 2 efflux surveys by the closed chamber circulation method at the Puhimau thermal area in the upper East Rift Zone (ERZ) of Kilauea volcano, Hawaii. The surveys were undertaken in 1996 and 1998 to constrain how much CO 2 might be reaching the ERZ after degassing beneath the summit caldera and whether the Puhimau thermal area might be a significant contributor to the overall CO 2 budget of Kilauea. The area was revisited in 2001 to determine the effects of surface disturbance on efflux values by the collar emplacement technique utilized in the earlier surveys. Utilizing a cutoff value of 50 g m −2 d −1 for the surrounding forest background efflux, the CO 2 emission rates for the anomaly at Puhimau thermal area were 27 t d −1 in 1996 and 17 t d −1 in 1998. Water vapor was removed before analysis in all cases in order to obtain CO 2 values on a dry air basis and mitigate the effect of water vapor dilution on the measurements. It is clear that Puhimau thermal area is not a significant contributor to Kilauea's CO 2 output and that most of Kilauea's CO 2 (8500 t d −1 ) is degassed at the summit, leaving only magma with its remaining stored volatiles, such as SO 2 , for injection down the ERZ. Because of the low CO 2 emission rate and the presence of a shallow water table in the upper ERZ that effectively scrubs SO 2 and other acid gases, Puhimau thermal area currently does not appear to be generally well suited for observing temporal changes in degassing at Kilauea.

Hawaii↗

USGS2006

The airborne lava-seawater interaction plume at Kilauea Volcano, Hawai'i

Lava flows into the sea at Kīlauea Volcano, Hawaiʻi, and generates an airborne gas and aerosol plume. Water (H 2 O), hydrogen chloride (HCl), carbon dioxide (CO 2 ), nitrogen dioxide (NO 2 ) and sulphur dioxide (SO 2 ) gases were quantified in the plume in 2004–2005, using Open Path Fourier Transform infra-red Spectroscopy. The molar abundances of these species and thermodynamic modelling are used to discuss their generation. The range in molar HCl / H 2 O confirms that HCl is generated when seawater is boiled dry and magnesium salts are hydrolysed (as proposed by [T.M. Gerlach, J.L. Krumhansl, R.O. Fournier, J. Kjargaard, Acid rain from the heating and evaporation of seawater by molten lava: a new volcanic hazard, EOS (Trans. Am. Geophys. Un.) 70 (1989) 1421–1422]), in contrast to models of Na-metasomatism. Airborne droplets of boiled seawater brine form nucleii for subsequent H 2 O and HCl condensation, which acidifies the droplets and liberates CO 2 gas from bicarbonate and carbonate. NO 2 is derived from the thermal decomposition of nitrates in coastal seawater, which takes place as the lava heats droplets of boiled seawater brine to 350–400 °C. SO 2 is derived from the degassing of subaerial lava flows on the coastal plain. The calculated mass flux of HCl from a moderate-sized ocean entry significantly increases the total HCl emission at Kīlauea (including magmatic sources) and is comparable to industrial HCl emitters in the United States. For larger lava ocean entries, the flux of HCl will cause intense local environmental hazards, such as high localised HCl concentrations and acid rain.

Hawaii↗

USGS2004

Evidence for dike emplacement beneath Iliamna Volcano, Alaska in 1996

Two earthquake swarms, comprising 88 and 2833 locatable events, occurred beneath Iliamna Volcano, Alaska, in May and August of 1996. Swarm earthquakes ranged in magnitude from -0.9 to 3.3. Increases in SO2 and CO2 emissions detected during the fall of 1996 were coincident with the second swarm. No other physical changes were observed in or around the volcano during this time period. No eruption occurred, and seismicity and measured gas emissions have remained at background levels since mid-1997. Earthquake hypocenters recorded during the swarms form a cluster in a previously aseismic volume of crust located to the south of Iliamna's summit at a depth of -1 to 4 km below sea level. This cluster is elongated to the NNW-SSE, parallel to the trend of the summit and southern vents at Iliamna and to the regional axis of maximum compressive stress determined through inversion of fault-plane solutions for regional earthquakes. Fault-plane solutions calculated for 24 swarm earthquakes located at the top of the new cluster suggest a heterogeneous stress field acting during the second swarm, characterized by normal faulting and strike-slip faulting with p-axes parallel to the axis of regional maximum compressive stress. The increase in earthquake rates, the appearance of a new seismic volume, and the elevated gas emissions at Iliamna Volcano indicate that new magma intruded beneath the volcano in 1996. The elongation of the 1996-1997 earthquake cluster parallel to the direction of regional maximum compressive stress and the accelerated occurrence of both normal and strike-slip faulting in a small volume of crust at the top of the new seismic volume may be explained by the emplacement and inflation of a subvertical planar dike beneath the summit of Iliamna and its southern satellite vents. ?? 2003 Elsevier B.V. All rights reserved.

Journal of Volcanology and Geothermal Research↗

USGS2003

Elevation effects in volcano applications of the COSPEC

Volcano applications commonly involve sizeable departures from the reference pressure and temperature of COSPEC calibration cells. Analysis shows that COSPEC SO2 column abundances and derived mass emission rates are independent of pressure and temperature, and thus unaffected by elevation effects related to deviations from calibration cell reference state. However, path-length concentrations are pressure and temperature dependent. Since COSPEC path-length concentration data assume the reference pressure and temperature of calibration cells, they can lead to large errors when used to calculate SO2 mixing ratios of volcanic plumes. Correction factors for COSPEC path-length concentrations become significant (c.10%) at elevations of about 1 km (e.g. Kilauea volcano) and rise rapidly to c.80% at 6 km (e.g. Cotopaxi volcano). Calculating SO2 mixing ratios for volcanic plumes directly from COSPEC path-length concentrations always gives low results. Corrections can substantially increase mixing ratios; for example, corrections increase SO2 ppm concentrations reported for the Mount St Helens, Colima, and Erebus plumes by 25-50%. Several arguments suggest it would be advantageous to calibrate COSPEC measurements in column abundance units rather than path-length concentration units.

Geological Society Special Publication↗

USGS2002

Carbon dioxide emission rate of Kīlauea Volcano: Implications for primary magma and the summit reservoir

We report a CO 2 emission rate of 8500 metric tons per day (t d −1 ) for the summit of Kīlauea Volcano, several times larger than previous estimates. It is based on three sets of measurements over 4 years of synchronous SO 2 emission rates and volcanic CO 2 /SO 2 concentration ratios for the summit correlation spectrometer (COSPEC) traverse. Volcanic CO 2 /SO 2 for the traverse is representative of the global ratio for summit emissions. The summit CO 2 emission rate is nearly constant, despite large temporal variations in summit CO 2 /SO 2 and SO 2 emission rates. Summit CO 2 emissions comprise most of Kīlauea's total CO 2 output (&sim;9000 t d −1 ). The bulk CO 2 content of primary magma determined from CO 2 emission and magma supply rate data is &sim;0.70 wt %. Most of the CO 2 is present as exsolved vapor at summit reservoir depths, making the primary magma strongly buoyant. Turbulent mixing with resident reservoir magma, however, prevents frequent eruptions of buoyant primary magma in the summit region. CO 2 emissions confirm that the magma supply enters the edifice through the summit reservoir. A persistent several hundred parts per million CO 2 anomaly arises from the entry of magma into the summit reservoir beneath a square kilometer area east of Halemaumau pit crater. Since most of the CO 2 in primary magma is degassed in the summit, the summit CO 2 emission rate is an effective proxy for the magma supply rate. Both scrubbing of SO 2 and solubility controls on CO 2 and S in basaltic melt cause high CO 2 /SO 2 in summit emissions and spatially uncorrelated distributions of CO 2 and SO 2 in the summit plume.

Journal of Geophysical Research B: Solid Earth↗

USGS2001

Soil efflux and total emission rates of magmatic CO2 at the horseshoe lake tree kill, mammoth mountain, California, 1995-1999

We report the results of eight soil CO2 efflux surveys by the closed circulation chamber method at the Horseshoe Lake tree kill (HLTK) - the largest tree kill on Mammoth Mountain. The surveys were undertaken from 1995 to 1999 to constrain total HLTK CO2 emissions and to evaluate occasional efflux surveys as a surveillance tool for the tree kills. HLTK effluxes range from 1 to > 10,000 g m -2 day -1 (grams CO2 per square meter per day); they are not normally distributed. Station efflux rates can vary by 7-35% during the course of the 8- to 16-h surveys. Disturbance of the upper 2 cm of ground surface causes effluxes to almost double. Semivariograms of efflux spatial covariance fit exponential or spherical models; they lack nugget effects. Efflux contour maps and total CO2 emission rates based on exponential, spherical, and linear kriging models of survey data are nearly identical; similar results are also obtained with triangulation models, suggesting that the kriging models are not seriously distorted by the lack of normal efflux distributions. In addition, model estimates of total CO2 emission rates are relatively insensitive to the measurement precision of the efflux rates and to the efflux value used to separate magmatic from forest soil sources of CO2. Surveys since 1997 indicate that, contrary to earlier speculations, a termination of elevated CO2 emissions at the HLTK is unlikely anytime soon. The HLTK CO2 efflux anomaly fluctuated greatly in size and intensity throughout the 1995-1999 surveys but maintained a N-S elongation, presumably reflecting fault control of CO2 transport from depth. Total CO2 emission rates also fluctuated greatly, ranging from 46 to 136 t day-1 (metric tons CO2 per day) and averaging 93 t day-1. The large inter-survey variations are caused primarily by external (meteorological) processes operating on time scales of hours to days. The externally caused variations can mask significant changes occurring at depth; a striking example is the masking of a degassing event generated at depth and detected by a soil gas sensor network in September 1997 while an efflux survey was in progress. Thus, occasional efflux surveys are not an altogether effective surveillance tool for the HLTK, and making them effective by greatly increasing their frequency may not be practical. Published by Elsevier Science B.V.

Chemical Geology↗

USGS2001

Implications for eruptive processes as indicated by sulfur dioxide emissions from Kilauea Volcano, Hawai'i, 1979-1997

Kı̄lauea Volcano, Hawai‘i, currently hosts the longest running SO 2 emission-rate data set on the planet, starting with initial surveys done in 1975 by Stoiber and his colleagues. The 17.5-year record of summit emissions, starting in 1979, shows the effects of summit and east rift eruptive processes, which define seven distinctly different periods of SO 2 release. Summit emissions jumped nearly 40% with the onset (3 January 1983) of the Pu`u `Ō`ō-Kūpaianaha eruption on the east rift zone (ERZ). Summit SO 2 emissions from Kı̄lauea showed a strong positive correlation with short-period, shallow, caldera events, rather than with long-period seismicity as in more silicious systems. This correlation suggests a maturation process in the summit magma-transport system from 1986 through 1993. During a steady-state throughput-equilibrium interval of the summit magma reservoir, integration of summit-caldera and ERZ SO 2 emissions reveals an undegassed volume rate of effusion of 2.1×10 5 m 3 /d. This value corroborates the volume-rate determined by geophysical methods, demonstrating that, for Kı̄lauea, SO 2 emission rates can be used to monitor effusion rate, supporting and supplementing other, more established geophysical methods. For the 17.5 years of continuous emission rate records at Kı̄lauea, the volcano has released 9.7×10 6 t (metric tonnes) of SO 2 , 1.7×10 6 t from the summit and 8.0×10 6 t from the east rift zone. On an annual basis, the average SO 2 release from Kı̄lauea is 4.6×10 5 t/y, compared to the global annual volcanic emission rate of 1.2×10 7 t/y.

Journal of Volcanology and Geothermal Research↗

USGS2001

Quiescent hydrogen sulfide and carbon dioxide degassing from Mount Baker, Washington

Volcanic H2S emission rate data are scant despite their importance in understanding magma degassing. We present results from direct airborne plume measurements of H2S and CO2 on a 21-orbit survey at eleven different altitudes around Mount Baker volcano in September 2000 utilizing instrumentation mounted in a light aircraft. Measured emission rates of H2S and CO2 were 5.5 td-1 and 187 td-1 respectively. Maximum concentrations of H2S and CO2 encountered within the 4-km-wide plume were 75 ppb and 2 ppm respectively. Utilizing the H2S signal as a marker for the plume allows the corresponding CO2 signal to be more easily and accurately distinguished from ambient CO2 background. This technique is sensitive enough for monitoring weakly degassing volcanoes in a pre-eruptive condition when scrubbing by hydrothermal fluid or aquifers might mask the presence of more acid magmatic gases such as SO2.

Geophysical Research Letters↗

USGS2000

Geochemical evidence for a magmatic CO 2 degassing event at Mammoth Mountain, California, September-December 1997

Recent time series soil CO 2 concentration data from monitoring stations in the vicinity of Mammoth Mountain, California, reveal strong evidence for a magmatic degassing event during the fall of 1997 lasting more than 2 months. Two sensors at Horseshoe Lake first recorded the episode on September 23, 1997, followed 10 days later by a sensor on the north flank of Mammoth Mountain. Direct degassing from shallow intruding magma seems an implausible cause of the degassing event, since the gas released at Horseshoe Lake continued to be cold and barren of other magmatic gases, except for He. We suggest that an increase in compressional strain on the area south of Mammoth Mountain driven by movement of major fault blocks in Long Valley caldera may have triggered an episode of increased degassing by squeezing additional accumulated CO 2 from a shallow gas reservoir to the surface along faults and other structures where it could be detected by the CO 2 monitoring network. Recharge of the gas reservoir by CO 2 emanating from the deep intrusions that probably triggered deep long-period earthquakes may also have contributed to the degassing event. The nature of CO 2 discharge at the soil-air interface is influenced by the porous character of High Sierra soils and by meteorological processes. Solar insolation is the primary source of energy for the Earth atmosphere and plays a significant role in most diurnal processes at the Earth surface. Data from this study suggest that external forcing due largely to local orographic winds influences the fine structure of the recorded CO 2 signals.

California↗

USGS1999

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

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.

Earth and Planetary Science Letters↗

USGS1998

Airborne volcanic plume measurements using a FTIR spectrometer, Kilauea volcano, Hawaii

A prototype closed-path Fourier transform infrared spectrometer system (FTIR), operating from battery power and with a Stirling engine microcooler for detector cooling, was successfully used for airborne measurements of sulfur dioxide at Kilauea volcano. Airborne profiles of the volcanic plume emanating from the erupting Pu′u′O′o vent on the East Rift of Kilauea revealed levels of nearly 3 ppm SO 2 in the core of the plume. An emission rate of 2,160 metric tons per day of sulfur dioxide was calculated from the FTIR data, which agrees closely with simultaneous measurements by a correlation spectrometer (COSPEC). The rapid spatial sampling possible from an airborne platform distinguishes the methodology described here from previous FTIR measurements.

Geophysical Research Letters↗

USGS1998

Three-year decline of magmatic CO2 emissions from soils of a Mammoth Mountain tree kill: Horseshoe Lake, CA, 1995-1997

We used the closed chamber method to measure soil CO 2 efflux over a three-year period at the Horseshoe Lake tree kill (HLTK)—the largest tree kill on Mammoth Mountain in central eastern California. Efflux contour maps show a significant decline in the areas and rates of CO 2 emission from 1995 to 1997. The emission rate fell from 350 t d −1 (metric tons per day) in 1995 to 130 t d −1 in 1997. The trend suggests a return to background soil CO 2 efflux levels by early to mid 1999 and may reflect exhaustion of CO 2 in a deep reservoir of accumulated gas and/or mechanical closure or sealing of fault conduits transmitting gas to the surface. However, emissions rose to 220 t d −1 on 23 September 1997 at the onset of a degassing event that lasted until 5 December 1997. Recent reservoir recharge and/or extension-enhanced gas flow may have caused the degassing event.

Geophysical Research Letters↗

USGS1998

Annual cycle of magmatic CO2 in a tree-kill soil at Mammoth Mountain, California: Implications for soil acidification

Time-series sensor data reveal significant short-term and seasonal variations of magmatic CO 2 in soil over a 12 month period in 1995–1996 at the largest tree-kill site on Mammoth Mountain, central-eastern California. Short-term variations leading to ground-level soil CO 2 concentrations hazardous and lethal to humans were triggered by shallow faulting in the absence of increased seismicity or intrusion, consistent with tapping a reservoir of accumulated CO 2 , rather than direct magma degassing. Hydrologic processes closely modulated seasonal variations in CO 2 concentrations, which rose to 65%–100% in soil gas under winter snowpack and plunged more than 25% in just days as the CO 2 dissolved in spring snowmelt. The high efflux of CO 2 through the tree-kill soils acts as an open-system CO 2 buffer causing infiltration of waters with pH values commonly of <4.2, acid loading of up to 7 keq H+ ṁha −1 ṁyr −1 , mobilization of toxic Al 3+ , and long-term decline of soil fertility.

Geology↗

USGS1994

Magmatic vapor source for sulfur dioxide released during volcanic eruptions: Evidence from Mount Pinatubo

Sulfur dioxide (SO2) released by the explosive eruption of Mount Pinatubo on 15 June 1991 had an impact on climate and stratospheric ozone. The total mass of SO2 released was much greater than the amount dissolved in the magma before the eruption, and thus an additional source for the excess SO2 is required. Infrared spectroscopic analyses of dissolved water and carbon dioxide in glass inclusions from quartz phenocrysts demonstrate that before eruption the magma contained a separate, SO2-bearing vapor phase. Data for gas emissions from other volcanoes in subduction-related arcs suggest that preeruptive magmatic vapor is a major source of the SO2 that is released during many volcanic eruptions.

Science↗

USGS1993

Oxygen buffering of Kilauea volcanic gases and the oxygen fugacity of Kilauea basalt

Volcanic gases collected during episode 1 of the Puu Oo eruption along the east rift zone of Kilauea Volcano, Hawaii, have uniform C-O-H-S-Cl-F compositions that are sharply depleted in CO 2 . The CO 2 -poor gases are typical of Type II volcanic gases ( gerlach and Graeber , 1985) and were emitted from evolved magma stored for a prolonged period of time in the east rift zone after releasing CO 2 -rich gases during an earlier period of temporary residence in the summit magma chamber. The samples are remarkably free of contamination by atmospheric gases and meteoric water. Thermodynamic evaluation of the analytical data shows that the episode 1 gases have equilibrium compositions appropriate for temperatures between 935 and 1032°C. Open- and closed-system equilibrium models of species distributions for the episode 1 gases show unequivocally that coexisting lavas buffered the gas oxygen fugacities during cooling. These models indicate that the f O 2 buffering process occurs by transfer of oxygen from the major species in the gas phase (H 2 O, CO 2 , SO 2 ) to the lava during cooling and that the transfer of oxygen also controls the fugacities of several minor and trace species (H 2 , CO, H 2 S, S 2 , Cl 2 , F 2 ), in addition to O 2 during cooling. Gas/lava exchanges of other components are apparently insignificant and exert little influence, compared to oxygen exchange, during cooling. Oxygen transfer during cooling is variable, presumably reflecting short-term fluctuations in gas flow rates. Higher flow rates restrict the time available for gas/lava oxygen transfer and result in gases with higher equilibrium temperatures. Lower flow rates favor f O 2 -constrained equilibration by oxygen transfer down to lower temperatures. Thus, the chemical equilibrium preserved in these gases is a heterogeneous equilibrium constrained by oxygen fugacity, and the equilibrium temperatures implied by the compositions of the gases reflect the temperatures at which gas/lava oxygen exchange ceased. This conclusion challenges the common assumption that volcanic gases are released from lava in a state of chemical equilibrium and then continue equilibrating homogeneously with falling temperature until reaction rates are unable to keep pace with cooling. No evidence is found, moreover, that certain gas species are kinetically more responsive and able to equilibrate down to lower temperatures than those of the last gas/lava oxygen exchange. Homogeneous reaction rates in the gas phase are apparently slow compared to the time it took for the gases to move from the last site of gas/lava equilibration to the site of collection. An earlier set of data for higher temperature CO 2 -rich Type I volcanic gases, which come from sustained summit lava lake eruptions supplied by magma that experienced substantially shorter periods of crustal storage, shows f O 2 buffering by oxygen transfer up to 1185°C. Oxygen fugacity measurements in drill holes into ponded lava flows suggest that buffering by oxygen transfer may control the f O 2 of residual gases down to several hundred degrees below the solidus in the early stages of cooling. Although the details of the f O 2 buffering mechanisms for oxygen transfer are unknown, the fact that f O 2 buffering is effective from molten to subsolidus conditions suggests that the reaction mechanisms must change with cooling as the reactants change from predominantly melt, to melt plus crystals, to glass plus crystals. Mass balance calculations suggest that redox reactions between the gas and ferrous/ferric iron in the lava are plausible mechanisms for the oxygen transfer and that the f O 2 of the gases is buffered by sliding ferrous/ferric equilibria in the erupting lavas. Contrary to expectations based on models predicting the oxidation of basalt by H 2 and CO escape during crustal storage, CO 2 -rich Type I gases and CO 2 -poor Type II gases have identical oxygen fugacities despite greatly different crustal storage and degassing histories. Volcanic gas data give a tightly constrained log f O 2 of NNO − 0.5 (±0.05) for subaerially erupted Kilauea basalt from liquidus to solidus temperatures, consistent with recent f O 2 determinations for the mantle source regions of ocean island basalts. Because the oxygen fugacities of volcanic gases emitted by subaerial lavas imply that the f O 2 of Kilauea basalt is unchanged during crustal storage, Kilauea basalt either arrives in the crust with an oxygen fugacity between NNO and FMQ, or it develops an oxygen fugacity in this range immediately upon arrival in the summit chamber.

Geochimica et Cosmochimica Acta↗