Halogen acids in fumarolic gases of Kilauea volcano

The water-rich condensates of fumarolic gases, obtained from degassing lavas of the 1959–60 eruption of Kilauea volcano, contain unexpectedly high concentrations of hydrofluoric and hydrochloric acids, and thereby suggest that halogens are significant constituents of basaltic magmas. Vents on the pumice hill of Kilauea Iki yielded one sample that contained, in parts per million, 21,000 HF (1.1 N) with 2,920 HCl, and another sample, 20 HF with 70,500 HCl (2.0 N). Samples from vents elsewhere on the volcano had from one-fortieth to one-thousandth as much of the two acids. A rough correlation exists between the temperature of the fumaroles (range 110 to 820°C) and the total concentration of the halogen acids. This correlation is mainly due to progressive dilution of the magmatic halogen acids by water of probable meteoric origin in fumaroles of lower temperatures. Variations in the HF/HCl ratio (range 0.0003 to 7.2) may be explained by means of two different processes whose relative importance cannot be assessed with the data at hand (1). In their migration to the surface, the acid gases may have reacted with the lava to a variable extent owing to the widely different configurations of the several vents (steaming areas in glassy pumice, glowing cracks, and drillhole in lava lake). In the reaction, relatively more HF could have reacted at temperatures around 300°C with the glassy pumice (2). There is some indication that the HF/HCl ratio increases with time,suggesting that the crystallizing lava may have released HCl early, with HF concentrated in the later exhalations. The Br/Cl ratio ranges from 0.0036 down to 0.0014, as compared to 0.0034 of seawater.     

Laboratory calibration of chemical volcanic gas sampling techniques using an artificial fumarole

We have constructed an artificial laboratory fumarole to calibrate the most common chemical volcanic gas sampling techniques and obtain a quantitative measure of their efficacy. We have also developed and tested a new rugged and portable venturi spray gas sampler. The venturi sampler reproduced the output gas composition most accurately, followed by the Giggenbach bottles, filter packs, and lastly alkaline traps. Passive alkaline traps, however, did better than filter packs when sampling more concentrated fumarole gases. Under ideal conditions, the accuracy of the Giggenbach bottles was identical to the venturi sampler, although there was slightly more scatter. The Giggenbach sampler was more susceptible to problems with condensation on the input train even in a laboratory setting, and this technique was only effective in relatively concentrated gas streams. Filter packs are also effective, but extreme care must be exercised to maintain strong undersaturation with respect to the acid gas. If strong undersaturation (high pH) is not maintained, the filter packs return erroneously low S/Cl and S/F ratios. Use of a pH indicator is an effective way of avoiding this problem. The passive alkaline traps also under-sample sulfur, resulting in low reported S/Cl and S/F ratios. It appears that the overall sampling efficiency of all techniques was not strongly affected by oxygen fugacity over the limited range tested. When detecting sulfate and sulfite simultaneously, we found no difference in total sulfur before and after oxidation. This suggests that all sulfur from the gas regardless of oxidation state was absorbed as sulfite or sulfate and/or was quickly oxidized in solution. This conclusion is supported by IC HS⁻ reference samples.     

Incrustations and fumarolic condensates at kilauea volcano, Hawaii: field, drill-hole and laboratory observations

Hawaiian volcanoes characteristically have but few of the many types of minerals found in incrustations of other volcanic areas. In Hawaii sulfates resulting from air oxidation of volatiles predominate, and fluorides produced during rock alteration by fumarolic gases are prominent. Halides are generally found where reducing conditions exist in fumaroles and lava lake drill holes. The most common mineral types are sulfur, opaline silica, gypsum, ralstonite, and thenardite. Minerals from the same deposit are found to vary markedly in the content of the less abundant components. Condensates from vapor issuing from fumaroles show little quantitative relationship in component content to incrustations deposited at the same fumaroles. It is believed that an energetically favorable isomorphic substitution of some elements in the crystal lattice of a depositing mineral may lead to the build-up of a high concentration of an element from a lean vapor. Equilibrium calculations applied to condensate studies give a good quantitative approximation to the concentrations of the elements found in natural systems, but when applied to incrustations they serve only to indicate general compositional relations. Laboratory studies have shown the important role of chlorides in metal transfer in the gas phase in high-temperature aqueous systems, but only in the absence of oxygen. These studies also demonstrated the important role of HF in rock alteration and in the transfer of silica.     

Temperature and heat flow measurements in a fumarolic area: Vulcano Island (Italy)

Vulcano, the southern Aeolian Island, is in fumarolic activity. The possibilities of measurements are limited by the field conditions as well as by the technological feasibility. In the presente work different tests were made in the field to measure temperature continuously: only the measurements made in dry steam gave good results because they avoid corrosion, and solution of the acid gases in the condensed in the ground. Field measurement show that the heat transfer is mainly due to convection. The values obtained in the field can be used to quantify the remote sensing of heat transfer.     

Origin of the fumarolic fluids of Vulcano Island,Italy and implications for volcanic surveillance

Variations in D and ¹⁸O values with H₂O contents and outlet temperatures indicate that the fumaroles of La Fossa crater have discharged mixtures of magmatic water and marine hydrothermal water, since 1979. The contribution of meteoric water was low in the period 1979–1982 and very low afterwards. The ¹⁸O values of the marine-hydrothermal component of +5 to +7.2 are due to isotopic exchange with the ¹⁸O-rich silicates of the rocks under high-temperature and low-permeability conditions. The ¹⁸O value of the magmatic end-member is generally +3.5 to +4.3, although values as high as +5.5 to +6.5 were reached in the summer of 1988, when magma degassing appears to have extended into the core of the magma body. The D values of the end-member were close to -20, typical of andesitic waters. Both the isotopic values and chemical data strongly support a dry model, consisting of a central magmatic gas column and a surrounding hydrothermal envelope, in which marine hydrothermal brines move along limited fracture zones to undergo total evaporation on approaching the conduits of magmatic fluids. The vents at the eastern and western boundaries of the fumarolic field are fed by fluids whose pressure is governed by the coexistence of vapor, liquid and halite, giving rise to a high risk of phreato magmatic explosions, should magma penetrate into these wet environments. Most La Fossa eruptions were triggered by an initial hydrothermal blast and continued with a series of phreatomagmatic explosions. The fluids discharged by the Forgia Vecchia fumaroles are mixed with meteoric water, which is largely evaporated, although subordinate loss of condensed steam may be responsible for scrubbing most of the acidic gas species. The temperatures and pressures, and the risk of a sudden pressure increase, are low. A boiling hydrothermal aquifer at 230° C is present underneath the Baia di Levante beach. This area has a minor risk of hydrothermal explosions.     

The geochemistry of thermal waters and fumarolic gases on Shiashkotan I., Kuril Islands

Based on geochemical studies we have updated our knowledge of the generation conditions and discharge of thermal waters on Shiashkotan Island. The thermal springs, which are abundant on the island, are surface expressions of the North Shiashkotan and Kuntomintar hydrothermal systems. The North Shiashkotan hydrothermal system shows the classical hydrochemical zonality. The discharge of the Kuntomintar hydrothermal system is confined within two thermal fields that are situated in the central and northeastern craters of the eponymous volcano. The high temperature of the gases that are issuing from Kuntomintar Volcano to the ground surface and the higher predictive ratios S/Cl, S/C, and CO₂/H₂ in its composition provide evidence of a possible renewal of its fumarole activity.     

New fumarolic activity on Mt. Baker: observations during April through July, 1975

On 10 March, 1975, large amounts of steam were first sighted coming from the Sherman Crater of Mt. Baker, long the site of mild fumarole activity. To document and evaluate the new activity, we conducted a series of aerial and ground-based observations and experiments including the collection of samples within the crater, installation of 35-mm automatic sequence cameras at Park and Anderson Buttes, and overflights with a mapping camera and infrared scanner. Significant changes characterizing the new activity are: development of a new, energetic fumarole in an area of earlier mild activity; growth of crevasses within and concentric to the crater walls; collapse of a central 70 m diameter plug of ice to form a warm lake; and ejection of tephra rich in analcite and sulfides from the new fumarole. Although the tephra contains minor amounts of unaltered glass, it does not differ in this or other respects from material collected from the west crater wall, where fumaroles have long been active. This suggests that the glass is older tephra derived from the fumarole vent walls.Weather and lighting conditions were such that the Park Butte sequence camera provided acceptable images of the crater area on 27% of the frames for the period 1825 Pacific Daylight Time June 5 to 1825 PDT August 2. Of these, 8% show a significant plume (>300 m above the vent). Large plumes occur during favorable weather conditions of low wind and high relative humidity, and all appear white.While there are abundant manifestations of increased heat emission from Sherman Crater, there is as yet no sign of a fundamental change in the style of activity, or that the rise of fresh magma is the cause.     

The magmatic- and hydrothermal-dominated fumarolic system at the Active Crater of Lascar volcano,northern Chile

Low-to-high temperature fumaroles discharging from the Active Crater of Lascar volcano (northern Chile) have been collected in November 2002, May 2005 and October 2006 for chemical and isotopic analysis to provide the first geochemical survey on the magmatic-hydrothermal system of this active volcano. Chemical and isotopic gas composition shows direct addition of high-temperature fluids from magmatic degassing, mainly testified by the very high contents of SO₂, HCl and HF (up to 87,800, 29,500 and 2,900 μmol/mol) and the high R/Ra values (up to 7.29). Contributions from a hydrothermal source, mainly in gas discharges of the Active Crater rim, has also been detected. Significant variations in fluid chemistry, mainly consisting of a general decrease of magmatic-related compounds, i.e. SO₂, have affected the fumarolic system during the period of observation, indicating an increase of the influence of the hydrothermal system surrounding the ascending deep fluids. The chemical composition of Active Crater fumaroles has been used to build up a geochemical model describing the main processes that regulate the fluid circulation system of Lascar volcano to be utilized in volcanic surveillance.     

Evolution of Br/Cl ratios in fumarolic salammoniac from Vulcano (Aeolian Islands,Italy)

 Bromine/chlorine ratios in salammoniac samples, collected from 1983 to 1994 at the Fossa crater fumaroles of Vulcano (Aeolian Islands), were determined. The data obtained in this work have been compared to those obtained by Coradossi et al. (1985) in order to carry out a systematic study of the Br/Cl ratio variations since 1977. Br/Cl ratios range from 0.04 to 0.29. The Br/Cl ratio variations observed have been interpreted as the result of different contributions among deep and shallow components feeding the fumarolic fluids of Vulcano. The Br/Cl increases, which occurred from 1977 to 1979, in 1983–1984 and in 1992–1993, have been connected to an increased input of magmatic gases. Received: 10 November 1995 / Accepted: 12 July 1996     

Evolution of fumarolic gases — boundary conditions set by measured parameters: case study at Vulcano,Italy

Physical, chemical and isotopic parameters were measured in fumaroles at the Vulcano crater and in drowned fumaroles near the beach. The data were used to define boundary conditions for possible conceptual models of the system.Crater fumaroles: time variations of CO₂ and SO₂ concentrations indicate mixing of saline gas-rich water with local fresh water. Cl/Br ratios of 300– 400 favour sea-water as a major source for Cl, Brand part of the water in the fumaroles. Cl concentrations and D values revealed, independently, amixing of 0.75 sea-water with 0.25 local freshwaterin furmarole F-5 during September 1982.Patterns of parameter correlation and mass balances reveal that CO₂, S, NH₃ and B originate from sources other than sea water. The CO₂ value of ¹³C = – 2%_o favours, at least partial, origin from decomposition of sedimentary rocks rather than mantle-derived material. Radiogenic⁴He(1.3 × lO^–3 ccSTP/g water) and radiogenic⁴⁰Ar(10.6 × 10^–4 ccSTP/g water) are observed, (⁴He/⁴⁰Ar)_radiogenic = 1.2, well in the range of values observed in geothermal systems.Drowned fumaroles: strongly bubbling gas at a pond and at the beachappears to have the same origin and initial compositionas the crater fumaroles (2 km away). The fumarolic gas is modified by depletion of the reactive gases, caused by dissolution in shallow-water. Atmospheric Ne, Ar, Kr and Xe are addeden route, some radiogenic He and Ar are maintained. The Vulcano system seems to be strongly influenced by the contribution of sea-water and decomposition of sedimentary rocks. Evidence of magmatic contributions is mainly derived from heat.     

取样瓶内球胆对水中溶解气测值影响的研究

引言 地下水中溶解气体的观测，在水文地质、水文地球化学、构造地球化学、环境保护等领域的水质调查研究中是一项经常做的项目。近20多年来，作为监测地震前兆的方法，更在国内外较广泛地开展起来，且取得了一些较好震例资料（张炜等，1992；蒋凤亮等，1989），在为各种目的所进行的溶解气体取样方法，多年来基本上都采用大口试剂瓶（内含球胆）作为取样、脱气装置（图1）。我们在实际工作中发现，这种取样装置内用来脱气的球胆对溶解气体总量及其组分等观测结果会有较大的影响。另外，还发现文献（地矿部地下水标准检验方法编写组，1988；…     

Genesis of chlorine and sulphur in fumarolic emissions at Vulcano Island (Italy): assessment of pH and redox conditions in the hydrothermal system

Chlorine- and sulphur-bearing compounds in fumarole discharges of the La Fossa crater at Vulcano Island (Italy) can be modelled by a mixing process between magmatic gases and vapour from a boiling hydrothermal system. This allows estimating the compounds in both endmembers. Magma degassing cannot explain the time variation of sulphur and HCl concentrations in the deep endmember, which are more probably linked to reactions of solid phases at depth, before mixing with the hydrothermal vapours. Based on the P–T conditions and speciation of the boiling hydrothermal system below La Fossa, the HCl and S_tot contents in the hydrothermal vapours were used to compute the redox conditions and pH of the aqueous solution. The results suggest that the haematite–magnetite buffer controls the hydrothermal fO₂ values, while the pH has increased since the end of the 1970s. The main processes affecting pH values may be linked to Na–Ca exchanges between evolved seawater, feeding the boiling hydrothermal system, and local rocks. While Na is removed from water, calcium enters the solution, undergoes hydrolysis and produces HCl, lowering the pH of the water. The increasing water–rock ratio within the hydrothermal system lowers the Ca availability, so the aqueous solution becomes less acidic. Seawater flowing towards the boiling hydrothermal brine dissolves a large quantity of pyrite along its path. In the boiling hydrothermal system, dissolved sulphur precipitates as pyrite and anhydrite, and becomes partitioned in vapour phase as H₂S and SO₂. These results are in agreement with the paragenesis of hydrothermal alteration minerals recovered in drilled wells at Vulcano and are also in agreement with the isotopic composition of sulphur emitted by the crater fumaroles.     

Extreme wave events and sampling variability

Ocean Dynamics - Wave field data are affected not only by the accuracy of instruments recording them but also by sampling variability, an uncertainty due to the limited number of observations. For...     

Geostatistical sampling optimization of contaminated facilities

Geostatistics applied to radiological evaluation of nuclear premises provides methods to estimate radiological activities, together with their associated uncertainty. It enables a sophisticated sampling methodology combining radiation map and destructive samples. The radiological assessment is divided in two steps: first, a regular control of the surface activity is performed. Then, to assess the true contamination, concrete samples are collected and analyses are performed at several locations within the premises. These two types of measurement are first dealt separately, then cokriging techniques are applied to estimate the contamination over the premise, taking both information into account. This paper presents a methodological study of geostatistical and computational approaches to target suitable areas for additional radiological measures. In order to compare the proposed augmented sampling designs, several optimization criteria are taken into account. Their diversity ensures the coverage of a wide range of real problematics. Two algorithms (greedy algorithm and simulated annealing) are developed to optimize the chosen criterion value as a function of the location of the additional points. The sampling scenarios obtained with the different algorithms are compared in terms of optimization performance and computational efficiency.     

Fumarole compositions and mercury emissions from the Tatun Volcanic Field,Taiwan: Results from multi-component gas analyser,portable mercury spectrometer and direct sampling techniques

Gas emissions from Tatun volcanic group, northern Taiwan, were studied for the first time using a multi-component gas analyser system (Multi-GAS) in combination with Giggenbach flask methods at fumaroles and mud pools at Da-you-keng (DYK) and Geng-tze-ping (GZP). CO₂/S molar ratios observed at DYK ranged from 3–17, similar ratios were observed using a Multi-GAS sensor box of 8–16. SO₂ at GZP was low, higher concentrations were observed at DYK where SO₂/H₂S ratios were close to 1 for both methods. A lower CO₂/H₂S ratio was measured via Giggenbach flask sampling (7.2) than was found in the plume using the gas sensor at GZP (9.2). This may reflect rapid oxidation of H₂S as it mixes with background air. Gaseous elemental mercury (GEM) levels were observed in the fumarole gases using a portable mercury spectrometer. These are the first such measurements of mercury at Tatun. Mean GEM concentrations in the fumarole plumes were ∼ 20 ng m^− 3, with much higher concentrations observed close to the ground (mean [GEM] 130 and 290 ng m^− 3 at DYK and GZP, respectively). The GEM in the fumarole plume was elevated above concentrations in industrial/urban air in northern Taiwan and the increase in GEM observed when the instrument was lowered suggests high levels of mercury are present in the surrounding ground surface. The GEM/CO₂ (10^− 8) and GEM/S (10^− 6) ratios observed in the fumarole gases were comparable to those observed at other low-temperature fumaroles. Combining the Hg/CO₂ ratio with a previous CO₂ flux value for the area, the annual GEM flux from the Tatun field is estimated as 5–50 kg/year.     

Chemical and isotopic variations in fumarolic discharge and thermal waters at Vulcano Island (Aeolian Islands, Italy) during 1996: evidence of resumed volcanic activity

Gas samples from some fumaroles at ‘La Fossa' crater and Baia di Levante on Vulcano Island and from a diffuse soil gas emission were analysed during 1995–1996, along with water samples from thermal wells in the area of Vulcano Porto. During 1996, we observed a significant increase both in the gas/steam ratio and in the CO₂ concentration, as well as strong variations in δ¹³C_CO2, δD_H2O and δ¹⁸O_H2O of fumarolic gases. These variations are probably related to an increased inflow of deep fluids of magmatic origin. The temperatures of fumaroles did not show remarkable variations except for fumarole F11. In this case, temperature increased by about 80°C from February to August 1996. During the same period, remarkable variations in temperature, phreatic level and chemical and isotopic composition of water were also recorded in one of the geothermal wells in the Vulcano Porto area (Camping Sicilia; T60°C). The observed variations in this well are probably related to a pressure build-up, occurring at least in the surficial part of the system, because of increased gas flux and/or decreased permeability of the fumarolic degassing system. Chemical and isotopic composition of the water showed that during this evolutionary phase, the content of fumarolic condensate in this well was about 80 to 90%. Based on the observation of physical and chemical variables of the Camping Sicilia fluids, during this phase of activity, it is concluded that this area is affected by a phreatic eruption hazard if a volcanic episode with high energy discharge in a limited time span occurs. It follows that this well may be considered as a preferential point for volcanic activity monitoring, both in the case of normal routine surveillance and in the case of inaccessibility to the crater area.