Imaging DOAS for volcanological applications

The simultaneous quantitative determination of two-dimensional bromine monoxide (BrO) and sulphur dioxide (SO₂) distributions in volcanic gas plumes is described. Measurements at the fumarolic field on the island Vulcano (autumn 2004) and in the plume of Mt. Etna volcano (spring 2005) were carried out with an Imaging DOAS instrument. The SO₂ fluxes of several fumaroles were estimated from two-dimensional distributions of SO₂. Additionally, the first two-dimensional distributions of BrO within a volcanic plume were successfully retrieved. Slant column densities of up to 2.6 × 10¹⁴ molecules per square centimetre were detected in the plume of Mt. Etna. The investigation of the BrO/SO₂ ratio, calculated from the two-dimensional distributions of SO₂ and BrO, shows an increase from the centre to the edge of the volcanic plume. These results have significance for the involvement of ozone during BrO formation processes in volcanic emissions.     

A new technique to estimate volcanic gas composition: plume measurements with a portable multi-sensor system

A portable multi-sensor system was developed to measure volcanic plumes in order to estimate the chemical composition and temperature of volcanic gases. The multi-sensor system consists of a humidity–temperature sensor, SO₂ electrochemical sensor, CO₂ IR analyzer, pump and flow control units, pressure sensor, data logger, and batteries; the whole system is light (∼5 kg) and small enough to carry in a medium-size backpack. Volcanic plume is a mixture of atmosphere and volcanic gas; therefore volcanic gas composition and temperature can be estimated by subtracting the atmospheric gas background from the plume data. In order to obtain the contrasting data of the plume and the atmosphere, measurements were repeated in and out of the plume. The multi-sensor technique was applied to measure the plume of Tarumae, Tokachi, and Meakan volcanoes, Hokkaido, Japan. Repeated measurements at each volcano gave a consistent composition with ±10–30% errors, depending on the stability of the background atmospheric conditions. Fumarolic gas samples were also collected at the Tokachi volcano by a conventional method, and we found a good agreement (the difference <10%) between the composition estimated by the multi-sensor technique and conventional method. Those results demonstrated that concentration ratios of major volcanic gas species (i.e., H₂O, CO₂, and SO₂) and temperature can be estimated by the new technique without any complicated chemical analyses even for gases emitted from an inaccessible open vent. Estimation of a more detailed gas composition can be also achieved by the combination of alkaline filter techniques to measure Cl/F/S ratios in the plume and other sensors for H₂S and H₂.     

Remote and in situ plume measurements of acid gas release from La Soufrière volcano, Guadeloupe

This paper presents the first remote measurements of La Soufrière gas emissions since the fumarolic and seismic reactivation in 1992. The chemical composition of the plumes has been measured from May 2003 to September 2004 using an Open Path Fourier Transform InfraRed (OP-FTIR) spectrometer, up to 15 m downwind the South Crater. HCl is clearly detected (concentration between 2.4 and 12 ppmv) whereas SO₂ and H₂S generally remain below the detection limit of the OP-FTIR. Direct measurements of SO₂ and H₂S near the South Crater with a Lancom III analyzer show a fast decrease of their concentrations with the distance. Calculated Cl / S mass ratios are high: from 9.4 ± 1.7 at 15 m from the vent to 2.8 ± 0.6 at 140 m. The enrichment in HCl of the gas emitted at La Soufrière, observed since 1998, corresponds to the degassing of a magma enriched in Cl and depleted in S. This result agrees with isotopic measurements which suggest a magmatic origin of the gases. Readjustments inside the volcanic system may have taken place during the seismic activity beginning in 1992 and enhance the transfer of magmatic gases to the summit.     

Radiative transfer corrections for accurate spectroscopic measurements of volcanic gas emissions

There is widespread use of passive remote sensing techniques to quantify trace gas column densities in volcanic plumes utilizing scattered sunlight as a light source. Examples include passive DOAS, COSPEC, and the SO₂ camera. In order to calculate trace gas concentrations or volcanic emission fluxes, knowledge about the optical path through the plume is necessary. In the past, a straight photon path through the plume has always been assumed although it was known that this is not always true. Here we present the results of model studies conducted specifically to quantify the effects of realistic radiative transfer in and around volcanic plumes on ground-based remote sensing measurements of SO₂. The results show that measurements conducted without additional information on average photon paths can be inaccurate under certain conditions, with possible errors spanning more than an order of magnitude. Both over and underestimation of the true column density can occur. Actual errors depend on parameters such as distance between instrument and plume, plume SO₂ concentration, plume aerosol load, as well as aerosol conditions in the ambient atmosphere. As an example, a measurement conducted with an SO₂ camera is discussed, the results of which can only be correctly interpreted if realistic radiative transfer is considered. Finally, a method is presented which for the first time allows the retrieval of actual average photon paths in spectroscopic (i.e. DOAS) measurements of adequate resolution. By allowing for a wavelength dependent column density during the evaluation of DOAS measurements, we show how radiative transfer effects can be corrected using information inherently available in the measured spectra, thus greatly enhancing the accuracy of DOAS measurements of volcanic emissions.     

Water chemistry of Lake Quilotoa (Ecuador) and assessment of natural hazards

A geochemical survey carried out in November 1993 revealed that Lake Quilotoa was composed by a thin (14 m) oxic epilimnion overlying a 200 m-thick anoxic hypolimnion. Dissolved CO₂ concentrations reached 1000 mg/kg in the lower stratum. Loss of CO₂ from epilimnetic waters, followed by calcite precipitation and a consequent lowering in density, was the apparent cause of the stratification.The Cl, SO₄ and HCO₃ contents of Lake Quilotoa are intermediate between those of acid–SO₄–Cl Crater lakes and those of neutral-HCO₃ Crater lakes, indicating that Lake Quilotoa has a ‘memory’ of the inflow and absorption of HC1- and S-bearing volcanic (magmatic) gases. The Mg/Ca ratios of the lake waters are governed by dissolution of local volcanic rocks or magmas, but K/Na ratios were likely modified by precipitation of alunite, a typical mineral in acid–SO₄–Cl Crater lakes.The constant concentrations of several conservative chemical species from lake surface to lake bottom suggest that physical, chemical and biological processes did not have enough time, after the last overturn, to cause significant changes in the contents of these chemical species. This lapse of time might be relatively large, but it cannot be established on the basis of available data. Besides, the lake may not be close to steady state. Mixing of Lake Quilotoa waters could presently be triggered by either cooling epilimnetic waters by 4°C or providing heat to hypolimnetic waters or by seismic activity.Although Quilotoa lake contains a huge amount of dissolved CO₂ (3×10¹¹ g), at present the risk of a dangerous limnic eruption seems to be nil even though some gas exsolution might occur if deep lake waters were brought to the surface. Carbon dioxide could build up to higher levels in deep waters than at present without any volcanic re-awakening, due to either a large inflow of relatively cool CO₂-rich gases, or possibly a long interval between overturns. Periodical geochemical surveys of Lake Quilotoa are, therefore, recommended.     

SO2 emission of the 1974 eruption of Volcán Fuego,Guatemala

Volcán Fuego in the Central American Republic of Guatemala erupted violently in October, 1974. A remote sensing correlation spectrometer. COSPEC IV, which utilizes the characteristic molecular absorption of SO₂ in the ultraviolet was used to monitor the SO₂ content of the volcanic plume. Over a 60-day period measurements were made on 37 days between and following major eruptive phases. SO₂ emission rates corrected for atmospheric scattering of the spectral signal average 423 metric tons/day with a standard deviation of 252 metric tons/days. Late stage peaks in SO₂ emission at Fuego are consistent with the presence of anomalously high contents of soluble materials on the stratigraphically highest ashes from other Central American eruptions. Indications are that the SO₂ concentration within the volcanic plume increased as activity waned. These features imply that remote spectroscopic sensing of SO₂ and perhaps other gases in a volcanic plume may provide a relatively easy and inexpensive means of determining the cessation of violent eruptive activity.     

A new collector for sampling volcanic aerosols

A new apparatus, Venturi Effect System (VES), designed for sampling volcanic plumes is described and tested at Vulcano (Italy). This device, together with purified basic NH₄OH solutions, supplies optimal conditions to obtain reliable S_total/Cl/F ratios and enrichment factors for metallic trace elements (MTE). Good concordance for acid gas ratios and metal enrichment factors in both the gas phase and the related plume allows the procedure to be validated. The VES appears in Vulcano conditions as a simple, robust and easily portable apparatus that allows reliable collection of both acid gases and MTE within a single sample and the analysis with current chemical methods (High Pressure Liquid Chromatography, Inductively Coupled Plasma–Mass Spectrometry). This apparatus may be suitable for more difficult volcanoes where only the plume can be sampled.     

The effects of volcanic ash on COSPEC measurements

Data from a series of laboratory experiments show the relationships between measured correlation spectrometer (COSPEC) sulfur-dioxide (SO₂) burdens, automatic gain control (AGC) deflections, and visible wavelength opacities in ash-laden plumes. The data show that the COSPEC reliably measures (within a 10% accuracy) SO₂ burdens up to AGC deflections of 2 V and visible wavelength opacities of 50%. Beyond these limits, the under measurement of the SO₂ burden is not well constrained. During typical COSPEC runs, these limits are rarely violated. The 10% error introduced by measuring ash-laden plumes is acceptable because the error is small relative to other error sources associated with the technique, especially plume velocity; and the error is correctable which allows for a wider range of plume conditions to be measured.These results imply that the densest SO₂ concentrations near the volcanic source can be measured. This is important so that SO₂ is not lost from the volcanic plume due to physical and chemical processes and that measurements are conducted under maximum signal to noise ratios.     

Evaluation of the Physical and Chemical Properties of Eyjafjallajökull Volcanic Plume Using a Cloud-Resolving Model

The Eyjafjallajökull volcanic eruption, which occurred on April 14, 2010, caused many environmental, air traffic and health problems. An attempt has been made to demonstrate for the first time that certain improvements could be made in the quantitative prediction of the volcanic ash parameters, and in the accounting of the processes in the immediate vicinity of the volcano, using a cloud-resolving model. This type of explicit modeling by treatment of volcanic ash and sulfate chemistry parameterization, with input of a number parameters describing the volcanic source, is the way forward for understanding the complex processes in plumes and in the future plume dispersion modeling. Results imply that the most significant microphysical processes are those related to accretion of cloud water, cloud ice and rainwater by snow, and accretion of rain and snow by hail. The dominant chemical conversion rates that give a great contribution to the sulfate budget are nucleation and dynamic scavenging and oxidation processes. A three-dimensional numerical experiment has shown a very realistic simulation of volcanic ash and other chemical compounds evolution, with a sloping structure strongly influenced by the meteorological conditions. In-cloud oxidation by H₂O₂ is the dominant pathway for SO₂ oxidation and allows sulfate to be produced within the SO₂ source region. The averaged cloud water pH of about 5.8 and rainwater pH of 4.5 over simulation time show quantitatively how the oxidation may strongly influence the sulfate budget and acidity of volcanic cloud. Compared to observations, model results are close in many aspects. Information on the near field volcanic plume behavior is essential for early preparedness and evacuation. This approach demonstrates a potential improvement in quantitative predictions regarding the volcanic plume distribution at different altitudes. It could be a useful tool for modeling volcanic plumes for better emergency measures planning.     

Chemistry and mineralogy of high-temperature gas discharges from Colima volcano, Mexico. Implications for magmatic gas–atmosphere interaction

Gases, condensates and silica tube precipitates were collected from 400°C (Z2) and 800°C (Z3) fumaroles at Colima volcano, Mexico, in 1996–1998. Volcanic gases at Colima were very oxidized and contain up to 98% air due to mixing with air inside the dome interior, close to the hot magmatic body. An alkaline trap method was used to collect gas samples, therefore only acidic species were analysed. Colima volcanic gases are water-rich (95–98 mol%) and have typical S/C/Cl/F ratios for a subduction type volcano. δD-values for the high-temperature Z3 fumarolic vapour vary from −26 to −57‰. A negative δD–Cl correlation for the Z3 high-temperature fumarole may result from magma degassing: enrichment in D and decrease in the Cl concentration in condensates are likely a consequence of input of “fresh” batches of magma and an increasing of volcanic activity, respectively.The trace element composition of Colima condensates generally does not differ from that of other volcanoes (e.g. Merapi, Kudryavy) except for some enrichment in V, Cu and Zn. Variations in chemical composition of precipitates along the silica tube from the high-temperature fumarole (Colima 1, fumarole Z3), in contrast to other volcanoes, are characterized by high concentrations of Ca and V, low concentration of Mo and a lack of Cd. Mineralogy of precipitates differs significantly from that described for silica tube experiments at other volcanoes with reduced volcanic gas. Thermochemical modelling was used to explain why very oxidized gas at Colima does not precipitate halite, sylvite, and Mo- and Cd-minerals, but does precipitate V-minerals and native gold, which have not been observed before in mineral precipitates from reduced volcanic gases.     

Gas composition of Popocatépetl Volcano between 2007 and 2008: FTIR spectroscopic measurements of an explosive event and during quiescent degassing

On December 1, 2007, the solar absorption infrared spectra of the Popocatépetl volcanic plume was recorded during an eruptive event and complementarily on November 17, 2008, the passive quiescent degassing was measured from the same site. A portable FTIR spectrometer with a scanning mirror for fast tracking of the sun provided the flexibility, quality, and simplicity needed for field deployment. Slant columns of the gases SO₂, HCl, HF, and SiF₄ were retrieved and strong differences could be observed when comparing gas ratios in both time periods. During the explosive eruption, the SO₂/HCl ratio was three times greater and the HF/HCl ratio was slightly smaller than during passive degassing.While the ratios among SO₂, HCl, HF, and SiF₄ describe the chemical composition of the volcanic gas mixture, the SiF₄/HF ratio provides information about the equilibrium temperatures of the stored gases which in this study were calculated at 150° and 185 °C for the explosive and quiescent degassing episodes, respectively. We conclude that cooling of lava domes in the crater precedes Vulcanian explosions as suggested by Schaaf et al (2005). Based on SO₂ flux (Grutter et al., 2008) and measurements and data from the November 2008 event, the average fluxes for HCl, HF, SiF₄, and F through quiescent degassing are estimated to be 204, 22.7, 9.8, and 31.7 tons/day, respectively. These values are similar to those reported by Love et al. (1998) more than 10 yrs ago.     

Summit CO2 emission rates by the CO2/SO2 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, Hawai?i, 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 SO₂ emission rates with synchronous CO₂/SO₂ ratios of the volcanic gas plume along the summit COSPEC traverse. The results are lower than the CO₂ 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 SO₂ pulses emitted adjacent to the COSPEC traverse, which biased CO₂/SO₂ ratios towards low values that may be unrepresentative of the global summit gas plume. We conclude that the SO₂ pulses are consequences of summit re-inflation under way since 2003 and that CO₂ emission rates remain comparable to, but more variable than, those measured prior to re-inflation.     

Accurately measuring volcanic plume velocity with multiple UV spectrometers

A fundamental problem with all ground-based remotely sensed measurements of volcanic gas flux is the difficulty in accurately measuring the velocity of the gas plume. Since a representative wind speed and direction are used as proxies for the actual plume velocity, there can be considerable uncertainty in reported gas flux values. Here we present a method that uses at least two time-synchronized simultaneously recording UV spectrometers (FLYSPECs) placed a known distance apart. By analyzing the time varying structure of SO₂ concentration signals at each instrument, the plume velocity can accurately be determined. Experiments were conducted on Kīlauea (USA) and Masaya (Nicaragua) volcanoes in March and August 2003 at plume velocities between 1 and 10 m s⁻¹. Concurrent ground-based anemometer measurements differed from FLYSPEC-measured plume speeds by up to 320%. This multi-spectrometer method allows for the accurate remote measurement of plume velocity and can therefore greatly improve the precision of volcanic or industrial gas flux measurements. Editorial responsibility: A. Woods     

Radionuclides and sulfur content in Mount Etna plume in 1983–1995: new constraints on the magma feeding system

Radionuclide activities (²¹⁰Pb, ²¹⁰Bi, ²¹⁰Po) were investigated in Mount Etna plume from 1983 to 1995. At SE crater the long-term observation (12 years) of the ²¹⁰Po/²¹⁰Pb ratio shows that it can behave as a degassing vent not directly related to the main magma reservoir depending on the magma level inside the volcano. Since 1992, the simultaneous determination of radionuclides and sulfur in the main plume results in new constraints on the degassing model of Lambert et al. (Earth Planet. Sci. Lett., 76 (1986) 185). The ²¹⁰Po/SO₂ and ²¹⁰Pb/SO₂ ratios enable us to identify two sources of ²¹⁰Po in the plume: one is magmatic, correlated with SO₂, the other one is an additional component issued from the decay of ²¹⁰Pb in the shallow degassing cell, and depends directly on the residence time of the gases before their emission. Estimations of the volume of degassing magma, the residence time of the gases and the proportion of undegassed magma renewing the shallow degassing cell are given for the period 1992–1995. During the 1992 eruption, the rate of degassing magma volume is estimated to have been as high as 5×10⁶ m³/day, and the volume of the shallow degassing magma reservoir about 0.5 km³. In 1994 and 1995 the rate of non-erupted degassing magma volume was estimated to have been about 0.18 km³/year. During the entire 1983–1995 period, only 15–20% of the degassed magma was erupted.     

Magmatic degassing at Erta 'Ale volcano,Ethiopia

Here we report measurements of the chemical composition and flux of gas emitted from the central lava lake at Erta 'Ale volcano (Ethiopia) made on 15 October 2005. We determined an average SO₂ flux of ∼ 0.69 ± 0.17 kg s^− 1 using zenith sky ultraviolet spectroscopy of the plume, and molar proportions of magmatic H₂O, CO₂, SO₂, CO, HCl and HF gases to be 93.58, 3.66, 2.47, 0.06, 0.19 and 0.04%, respectively, by open-path Fourier transform infrared (FTIR) spectrometry. Together, these data imply fluxes of 7.3, 0.7, 0.008, 0.03 and 0.004 kg s^− 1 for H₂O, CO₂, CO, HCl and HF, respectively. These are the first FTIR spectroscopic observations at Erta 'Ale, and are also some of the very few gas measurements made at the volcano since the early 1970s (Gerlach, T.M., 1980b. Investigation of volcanic gas analyses and magma outgassing from Erta 'Ale lava lake, Afar, Ethiopia. Journal of Volcanology and Geothermal Research, 7(3–4): 415–441). We identify significant increases in the proportion of H₂O in the plume with respect to both CO₂ and SO₂ across this 30-year interval, which we attribute to the depletion of volatiles in magma that sourced effusive eruptions during the early 1970s and/or to fractional magma degassing between the two active pit craters located in the summit caldera.     

Geochemical mapping of magmatic gas–water–rock interactions in the aquifer of Mount Etna volcano

Systematic analysis of major and minor elements in groundwaters from springs and wells on the slopes of Mt. Etna in 1995–1998 provides a detailed geochemical mapping of the aquifer of the volcano and of the interactions between magmatic gas, water bodies and their host rocks. Strong spatial correlations between the largest anomalies in pCO₂ (pH and alkalinity) K, Rb, Mg, Ca and Sr suggest a dominating control by magmatic gas (CO₂) and consequent basalt leaching by acidified waters of the shallow (meteoric) Etnean aquifer. Most groundwaters displaying this magmatic-type interaction discharge within active faulted zones on the S–SW and E lower flanks of the volcanic pile, but also in a newly recognised area on the northern flank, possibly tracking a main N–S volcano-tectonic structure. In the same time, the spatial distribution of T°C, TDS, Na, Li, Cl and B allows us to identify the existence of a deeper thermal brine with high salinity, high content of B, Cl and gases (CO₂, H₂S, CH₄) and low K/Na ratio, which is likely hosted in the sedimentary basement. This hot brine reaches the surface only at the periphery of the volcano near the Village of Paternò, where it gives rise to mud volcanoes called “Salinelle di Paternò”. However, the contribution of similar brines to shallower groundwaters is also detected in other sectors to the W (Bronte, Maletto), SW (Adrano) and SE (Acireale), suggesting its possible widespread occurrence beneath Etna. This thermal brine is also closely associated with hydrocarbon fields all around the volcano and its rise, generally masked by the high outflow of the shallow aquifer, may be driven by the ascent of mixed sedimentary–magmatic gases through the main faults cutting the sedimentary basement.     

Geochemistry of the magmatic–hydrothermal system of Kawah Ijen volcano, East Java, Indonesia

Samples from Kawah Ijen crater lake, spring and fumarole discharges were collected between 1990 and 1996 for chemical and isotopic analysis. An extremely low pH (<0.3) lake contains SO₄–Cl waters produced during absorption of magmatic volatiles into shallow ground water. The acidic waters dissolve the rock isochemically to produce “immature” solutions. The strong D and ¹⁸O enrichment of the lake is mainly due to enhanced evaporation at elevated temperature, but involvement of a magmatic component with heavy isotopic ratios also modifies the lake D and ¹⁸O content. The large Δ_SO4–S⁰ (23.8–26.4‰) measured in the lake suggest that dissolved SO₄ forms during disproportionation of magmatic SO₂ in the hydrothermal conduit at temperatures of 250280°C. The lake δ¹⁸O_SO4 and δ¹⁸O_H2O values may reflect equilibration during subsurface circulation of the water at temperatures near 150°C. Significant variations in the lake's bulk composition from 1990 to 1996 were not detected. However, we interpret a change in the distribution and concentration of polythionate species in 1996 as a result of increased SO₂-rich gas input to the lake system.Thermal springs at Kawah Ijen consist of acidic SO₄–Cl waters on the lakeshore and neutral pH HCO₃–SO₄–Cl–Na waters in Blawan village, 17 km from the crater. The cation contents of these discharges are diluted compared to the crater lake but still do not represent equilibrium with the rock. The SO₄/Cl ratios and water and sulfur isotopic compositions support the idea that these springs are mixtures of summit acidic SO₄–Cl water and ground water.The lakeshore fumarole discharges (T=170245°C) have both a magmatic and a hydrothermal component and are supersaturated with respect to elemental sulfur. The apparent equilibrium temperature of the gas is 260°C. The proportions of the oxidized, SO₂-dominated magmatic vapor and of the reduced, H₂S-dominated hydrothermal vapor in the fumaroles varied between 1979 and 1996. This may be the result of interaction of SO₂-bearing magmatic vapors with the summit acidic hydrothermal reservoir. This idea is supported by the lower H₂S/SO₂ ratio deduced for the gas producing the SO₄–Cl reservoir feeding the lake compared with that observed in the subaerial gas discharges. The condensing gas may have equilibrated in a liquid–vapor zone at about 350°C.Elemental sulfur occurs in the crater lake environment as banded sediments exposed on the lakeshore and as a subaqueous molten body on the crater floor. The sediments were precipitated in the past during inorganic oxidation of H₂S in the lake water. This process was not continuous, but was interrupted by periods of massive silica (poorly crystallized) precipitation, similar to the present-day lake conditions. We suggest that the factor controlling the type of deposition is related to whether H₂S- or silica-rich volcanic discharges enter the lake. This could depend on the efficiency with which the lake water circulates in the hydrothermal cell beneath the crater. Quenched liquid sulfur products show δ³⁴S values similar to those found in the banded deposits, suggesting that the subaqueous molten body simply consists of melted sediments previously accumulated at the lake bottom.     

The chemical and hydrologic structure of Poa´s Volcano, Costa Rica

Comparison of the chemical characteristics of spring and river water draining the flanks of Poa´s Volcano, Costa Rica indicates that acid chloride sulfate springs of the northwestern flank of the volcano are derived by leakage and mixing of acid brines formed in the summit hydrothermal system with dilute flank groundwater. Acid chloride sulfate waters of the Rio Agrio drainage basin on the northwestern flank are the only waters on Poa´s that are affected by leakage of acid brines from the summit hydrothermal system. Acid sulfate waters found on the northwestern flank are produced by the interaction of surface and shallow groundwater with dry and wet acid deposition of SO₂ and H₂SO₄ aerosols, respectively. The acid deposition is caused by a plume of acid gases that is released by a shallow magma body located beneath the active crater of Poa´s.No evidence for a deep reservoir of neutral pH sodium chloride brine is found at Poa´s. The lack of discharge of sodium chloride waters at Poa´s is attributed to two factors: (1) the presence of a relatively volatile-rich magma body degassing at shallow depths (< 1 km) into a high level summit groundwater system; and (2) the hydrologic structure of the volcano in which high rates of recharge combine with rapid lateral flow of shallow groundwater to prevent deep-seated sodium chloride fluids from ascending to the surface. The shallow depth of the volatile-rich magma results in the degassing of large quantities of SO₂ and HCl. These gases are readily hydrolyzed and quickly mix with meteoric water to form a reservoir of acid chloride-sulfate brine in the summit hydrothermal system. High recharge rates and steep hydraulic gradients associated with elevated topographic features of the summit region promote lateral flow of acid brines generated in the summit hydrothermal system. However, the same high recharge rates and steep hydraulic gradients prevent lateral flow of deep-seated fluids, thereby masking the presence of any sodium chloride brines that may exist in deeper parts of the volcanic edifice.Structural, stratigraphic, and topographic features of Poa´s Volcano are critical in restricting flow of acid brines to the northwestern flank of the volcano. A permeable lava-lahar sequence that outcrops in the Rio Agrio drainage basin forms a hydraulic conduit between the crater lake and acid chloride sulfate springs. Spring water residence times are estimated from tritium data and indicate that flow of acid brines from the active crater to the Rio Agrio source springs is relatively rapid (3 to 17 years). Hydraulic conductivity values of the lava-lahar sequence calculated from residence time estimates range from 10⁻⁵ to 10⁻⁷ m/s. These values are consistent with hydraulic conductivity values determined by aquifer tests of fractured and porous lava/pyroclastic sequences at the base of the northwestern flank of the volcano.Fluxes of dissolved rock-forming elements in Rio Agrio indicate that approximately 4300 and 1650 m³ of rock are removed annually from the northwest flank aquifer and the active crater hydrothermal system, respectively. Over the lifetime of the hydrothermal system (100's to 1000's of years), significant increases in aquifer porosity and permeability should occur, in marked contrast to the reduction in permeability that often accompanies hydrothermal alteration in less acidic systems. Average fluxes of fluoride, chloride and sulfur calculated from discharge and compositional data collected in the Rio Agrio drainage basin over the period 1988–1990 are approximately 2, 38 and 30 metric tons/day. These fluxes should be representative of minimum volatile release rates at Poa´s in the last 10 to 20 years.     

Chemical changes in spring waters at Tacaná volcano, Chiapas, Mexico: A possible precursor of the May 1986 seismic crisis and phreatic explosion

Local seismic activity consisting of sharp earthquakes accompanied by thunderous noise was reported starting in late December 1985 around Tacaná volcano (15.13°N, 92.10°W). Portable seismic stations were established in the area by late January 1986 and sampling of the only known thermal spring on the volcano flanks started at the same time. A marked increase in SO₄²⁻ concentration in the spring water preceded by two months the occurrence of a seismic swarm crisis and a small phreatic explosion. A model involving a crystalline basement fractured by tectonic stresses is proposed to explain the chemical and seismic anomalies, and the consequences on risk of volcanic activity are briefly discussed in terms of the observed behaviour.     

Evaluation of volcanic gas analysis from surtsey volcano, iceland 1964–1967

Methods used previously to remove compositional modifications from volcanic gas analyses for Mount Etna and Erta'Ale lava lake have bean employed to estimate the gas phase composition at Nyiragongo lava lake, based on samples obtained in 1959. H₂O data were not reported in 11 of the 13 original analyses. The restoration methods have been used to estimate the H₂O contents of the samples and to correct the analyses for atmospheric contamination, loss of sulfur and for pre- and pest-collection oxidation of H₂S, S₂, and H₂. The estimated gas compositions are relatively CO₂-rich, low in total sulfur and reduced. They contain approximately 35–50% CO₂ 45–55% H₂O, 1–2% SO₂, 1–2% H₂., 2–3% CO, 1.5–2.5% H₂S, 0.5% S₂ and 0.1% COS over,he collection temperature range 102° to 960° C. The oxygen fugacities of the gases are consistently about half an order of magnitude below quartz-magnetite-fayalite. The low total sulfur content and resulting low atomic S/C of the Nyiragongo gases appear to be related to the relatively low f_O2 of the crystallizing lava. At temperatures above 800°C and pressures of 1–1.5 k bar, the Nyiragongo gas compositions resemble those observed in primary fluid inclusions believed to have formed at similar temperatures and pressures in nephelines of intrusive alkaline rocks. Cooling to 300°C, with f_O2 buffered by the rock, results in gas compositions very rich in CH₄ (50–70%) and resembling secondary fluid inclusions formed at 200–500°C in alkaline rocks. Below 600°C the gases become supersaturated in carbon as graphite. These inferences are corroborated by several reports of hydrocarbons in plutonic alkaline rocks, and by the presence of CH₄-rich waters in Lake Kivu — a lake on the flanks of Nyiragongo volcano.