Diffuse volcanic degassing and thermal energy release from Hengill volcanic system, Iceland

We report the first detailed study of spatial variations on the diffuse emission of carbon dioxide (CO₂) and hydrogen sulfide (H₂S) from Hengill volcanic system, Iceland. Soil CO₂ and H₂S efflux measurements were performed at 752 sampling sites and ranged from nondetectable to 17,666 and 722?g?m^?2?day^?1, respectively. The soil temperature was measured at each sampling site and used to evaluate the heat flow. The chemical composition of soil gases sampled at selected sampling sites during this study shows they result from a mixing process between deep volcanic/hydrothermal component and air. Most of the diffuse CO₂ degassing is observed close to areas where active thermal manifestations occur, northeast flank of the Hengill central volcano close to the Nesjavellir power plant, suggesting a diffuse degassing structure with a SSW?CNNE trend, overlapping main fissure zone and indicating a structural control of the degassing process. On the other hand, H₂S efflux values are in general very low or negligible along the study area, except those observed at the northeast flank of the Hengill central volcano, where anomalously high CO₂ efflux and soil temperatures were also measured. The total diffuse CO₂ emission estimated for this volcanic system was about 1,526?±?160?t?day^?1 of which 453?t?day^?1 (29.7?%) are of volcanic/hydrothermal origin. To calculate the steam discharge associated with the volcanic/hydrothermal CO₂ output, we used the average H₂O/CO₂ mass ratio from 12 fumarole samples equal to 88.6 (range, 9.4?C240.2) as a representative value of the H₂O/CO₂ mass ratios for Hengill fumarole steam. The resulting estimate of the steam flow associated with the gas flux is equal to 40,154?t?day^?1. The condensation of this steam results in thermal energy release for Helgill volcanic system of 1.07?×?10¹⁴?J?day^?1 or to a total heat flow of 1,237?MW_t.     

Content and behavior of fluorine in Japanese quaternary volcanic rocks and petrogenetic application

Fluorine contents in about 160 representative Quaternary volcanic rocks and 15 hornblende and biotite phenocrysts in a calc-alkali series in Japan have been determined by a selective ion-electrode method. Tholeiites have the lowest contents and the narrowest range (58–145 ppm), while alkali basalts have the highest contentws and the widest range (301–666 ppm), high-alumina basalts have intermediate values (188–292 ppm). F contents in basalts clearly increase from east to west across the Japanese Islands, as do alkalies, P₂O₅ REE, U, Th and H₂O.The volcanic rocks studied are divided into two groups on the basis of F: (1) witt, increasing % SiO₂ or advancing fractionation, F contents show either progressive enrichment; or (2) with increasing fractionation, F contents show rather constant values. The former is produced by fractionation of anhydrous phases from basalt to mafic andesite magmas; the tholeiite series of Nasu volcanic zone (outer zone), northeastern, Japan is a typical example. The latter group is derived through separation of amphibole-bearing phases from basaltic magmas at various depths from upper mantle (about 30 km) to upper crust; the alkali series in southwestern Japan and the calc-alkali series of Chokai volcanic zone (inner zone), northeastern Japan, are examples.     

Defining hydrochemical evolution of streamflow through flowpath dynamics in Kawakami headwater catchment,Central Japan

The hydrochemical behaviour of catchments is often investigated by inferring stream chemistry through identification of source areas involved in hydrograph separation analysis, yet its dynamic evolution of hydrologic pathways has received little attention. Intensive hydrometric and hydrochemical measurements were performed during two different storms on March 29, 2001 and August 21–22, 2001 to define hydrochemical evolution under the dynamic of flow pathways in a 5·2 ha first‐order drainage of the Kawakami experimental basin (KEB), Central Japan, a forested headwater catchment with various soil depths (1·8 to 5 m) overlying late Neogene of volcanic bedrocks. The hydraulic potential distribution and flow lines data showed that the change in flow direction, which was controlled by rainfall amount and antecedent wetness of the soil profile, agreed well with the hydrochemical change across the slope segment during the storm. Hydrograph separation predicted by end‐member mixing analysis (EMMA) using Ca²⁺ and SiO₂ showed that near surface riparian, hillslope soil water and deep riparian groundwater were important in stream flow generation. The evidence of decrease in solutes concentration at a depth of 1 m in the hillslope and 0·6 m in the near surface riparian during peak storm suggested a flushing of high solutes concentration. Most of the solutes accumulated in the deep riparian groundwater zone, which was due to prominent downward flow and agreed well with the residence time. The distinct flow pathways and chemistry between the near surface riparian and deep riparian groundwater zones and the linkage hillslope aquifer and near surface riparian reservoir, which controls rapid flow and solutes flushing during the storm event, are in conflict with the typical assumption that the whole riparian zone resets flow pathways and chemical signature of hillslope soil water, as has been reported in a previous study. Copyright © 2005 John Wiley & Sons, Ltd.     

Outline volcanic history of the region west of Vatnajökull, Central Iceland

This paper outlines the structure and volcanic geology of a 25 × 50 km region of central Iceland including part of the eastern neovolcanic zone and its western margin. It includes an extinct Brunhes epoch silicic centre, the Hagangas, offset en échelon from a zone of major postglacial basaltic activity forming a northeasterly extension of the Torfajökull centre. Stratigraphic subdivisions restricted to the last 690,000 years comprise, in order of decreasing age, interglacial flood tholeiites, major centres of intraglacial hyaloclastite eruption, and postglacial lavas, which are mostly olivine basalts. The Hagangas centre and interglacial tholeiites lie on crust predominantly of Matuyama age (0.69–2.30 m.y.) but the bulk of the present volcanic activity may be taking place through crust belonging entirely to the present polarity epoch; this latter zone is characterised by normal faulting and extensive hydrothermal alteration. The widespread hydrothermal alteration and voluminous basaltic eruption distinguish this neovolcanic zone from the western zone, and the relationship of the region to growth of the upper crust in Iceland is briefly discussed.     

Holocene eruptive history of Ksudach volcanic massif,South Kamchatka: evolution of a large magmatic chamber

The combination of geological, tephrochronological and geochemical studies is used to reconstruct the Holocene eruptive history of Ksudach volcanic massif, South Kamchatka and to trace the evolution of its magma. Ksudach is located in the frontal volcanic zone of Kamchatka. From Early Holocene till AD 240, the volcano had repetitive voluminous caldera-forming eruptions. Later they gave way to frequent moderate explosive–effusive eruptions that formed the Shtyubel' stratovolcano inside the nested calderas, and then to frequent larger explosive eruptions. Holocene eruptive products are low-K₂O two pyroxene–plagioclase basaltic andesite to rhyodacite. Mineralogical, geochemical and isotopic data suggest that all the rock varieties originated as a result of fractionation of an initial mafic melt, with insignificant contamination and assimilation. Intensive mixing of the fractionating melts prior to, and during the course of the eruptions, is ubiquitous. The eruptions might have been triggered by repetitive injections of new mafic melt into the silicic chamber. Crystallization of the andesitic and rhyodacitic melts is estimated to have occurred at temperatures of 970–1010°C and 890–910°C, respectively, P_H2O 1.5–2.0 kbar and f_O2 close to the NNO buffer. According to the experimental data, such P_H2O corresponds to 4.5%–5.5% of water in the melt, that is close to the content of water in the silicic hornblende-bearing magmas of the rear zone of the Kuril–Kamchatka arc. Hence, we suggest that the transition from pyroxene phenocryst associations of the frontal zone to the hornblende-bearing ones of the rear zone might be interpreted as reflecting higher temperatures of crystallization of the melts from the frontal zone rather than increasing water content in the rear zone magmas.     

Patterns of groundwater hydrochemistry in Apan-Tochac sub-basin,Mexico

Abstract

On the basis of the degree of mineralization, the groundwater of Apan-Tochac sub-basin may be considered as fresh (TDS < 500 ppm). However, chlorination is necessary to make it fit for human consumption. Major ion analyses of over 235 water samples reveal a striking relationship between hydrochemical evolution and the groundwater flow system. A high content of total dissolved solids, and low values of the Ca:Mg ratio are present in wells located on the plain (discharge zone), whereas opposite conditions are associated with wells located in higher regions (recharge zone). Statistical data analysis using the method of principal components allowed to differentiation of two hydrochemical families: (a) low mineralization corresponding to the recharge zone, and (b) high mineralization corresponding to the discharge zone. Waters of the Ca + Mg + HCO₃, and Na + Mg + HCO₃ hydrochemical fades are present and the former is dominant. The water is slightly alkaline, having slight problems of salinity during the year owing mainly to Ca²⁺HCO₃ ^? and Na⁺Cl^? salts. The hydrochemistry of the groundwater reflects the pattern of local groundwater flow for this sub-basin.     

Contributing sources to baseflow in pre‐alpine headwaters using spatial snapshot sampling

Mountainous headwaters consist of different landscape units including forests, meadows and wetlands. In these headwaters it is unclear which landscape units contribute what percentage to baseflow. In this study, we analysed spatiotemporal differences in baseflow isotope and hydrochemistry to identify catchment‐scale runoff contribution. Three baseflow snapshot sampling campaigns were performed in the Swiss pre‐alpine headwater catchment of the Zwäckentobel (4.25 km²) and six of its adjacent subcatchments. The spatial and temporal variability of δ²H, Ca, DOC, AT, pH, SO₄, Mg and H₄SiO₄ of streamflow, groundwater and spring water samples was analysed and related to catchment area and wetland percentage using bivariate and multivariate methods. Our study found that in the six subcatchments, with variable arrangements of landscape units, the inter‐ and intra catchment variability of isotopic and hydrochemical compositions was small and generally not significant. Stream samples were distinctly different from shallow groundwater. An upper spring zone located near the water divide above 1,400 m and a larger wetland were identified by their distinct spatial isotopic and hydrochemical composition. The upstream wetland percentage was not correlated to the hydrochemical streamflow composition, suggesting that wetlands were less connected and act as passive features with a negligible contribution to baseflow runoff. The isotopic and hydrochemical composition of baseflow changed slightly from the upper spring zone towards the subcatchment outlets and corresponded to the signature of deep groundwater. Our results confirm the need and benefits of spatially distributed snapshot sampling to derive process understanding of heterogeneous headwaters during baseflow. Copyright © 2015 John Wiley & Sons, Ltd.     

A preliminary stable isotope study of volcanic ashes discharged by the 1979 eruption of Ontake Volcano,Nagano, Japan

Sulphur isotopic compositions of pyrite, anhydrite and native sulphur in volcanic ashes discharged by the 1979 eruption of Ontake volcano, Nagano, Japan were determined. The isotopic data indicate that sulphate in anhydrite and a part of native sulphur were produced by the disproportionation reaction of sulphite formed by dissolution of SO₂ in volcanic gases into water which filled a mud reservoir probably located just below the crater zone. Some part of H₂S in volcanic gases was fixed as pyrite and some was oxidised to form native sulphur. Hydrothermal alteration of country rocks to form pyrite, anhydrite and clay minerals had proceeded in the mud reservoir before eruption at temperatures ranging from 110° to 185°C which were estimated by oxygen isotopic fractionation between anhydrite and water.

     

Lateral variations of H2O contents in quaternary magmas of Northeastern Japan

Volcanoes of the East Japan volcanic arc are divided into two groups on the basis of their phenocryst assemblages; volcanoes with lavas or pyroclastic rocks containing quartz phenocrysts and no hornblende phenocrysts (type A), and those with rocks containing hornblende phenocrysts and no quartz phenocrysts (type B). Type A volcanoes occur only in the narrow region along the volcanic front, whereas type B volcanoes are distributed in the area closer to the Sea of Japan.Recent experimental studies on calc-alkaline andesite-dacite under H₂O-saturated and -undersaturated conditions indicate that the liquidus temperature (maximum thermal stability limit) of quartz decreases drastically with increasing H₂O content in magma, whereas the liquidus temperatures of hornblende and biotite are relatively constant with variations in the H₂O content and bulk chemical composition of the magma.It is suggested from the lateral variation of mafic phenocryst assemblages [1] and from the above result that the temperature of the parental magmas of these volcanoes increases, and their H₂O contents decrease, towards the volcanic front in the East Japan volcanic arc.Such lateral variations in the H₂O contents of magmas under the East Japan volcanic arc are in agreement with those of other incompatible elements (K, Rb, REE, etc.). If H₂O-undersaturated partial melting of upper mantle peridotite can be represented by the univariant line (olivine, Ca-rich clinopyroxene, orthopyroxene and liquid coexist) in the system H₂OMg₂SiO₄z.sbnd;CaMgSi₂O₆z.sbnd;SiO₂, the decrease of H₂O content in the magma suggests that the melting temperature of the peridotitic mantle may gradually increase, and so the degree of partial melting may increase, towards the volcanic front. The lateral variation of other incompatible elements can also be explained by this model.     

Isotopic geochemistry of acid thermal waters and volcanic gases from Zaō volcano in Japan

The chemical composition and D/H, and ratios have been determined for the acid hot waters and volcanic gases discharging from Zaō volcano in Japan. The thermal springs in Zaō volcano issue acid sulfate-chloride type waters (Zaō) and acid sulfate type waters (Kamoshika). Gases emitted at Kamoshika fumaroles are rich in CO₂, SO₂ and N₂, exclusive of H₂O. Chloride concentrations and oxygen isotope data indicate that the Zaō thermal waters issue a fluid mixture from an acid thermal reservoir and meteoric waters from shallow aquifers. The waters in the Zaō volcanic system have slight isotopic shifts from the respective local meteoric values. The isotopic evidence indicates that most of the water in the system is meteoric in origin. Sulfates in Zaō acid sulfate-chloride waters with δ³⁴S values of around +15‰, are enriched in ³⁴S compared to Zaō H₂S, while the acid sulfate waters at Kamoshika contain supergene light sulfate (δ³⁴S = + 4‰) derived from volcanic sulfur dioxide from the volcanic exhalations. The sulfur species in Zaō acid waters are lighter in δ³⁴S than those of other volcanic areas, reflecting the difference in total pressure.     

Coseismic changes in the chemical composition of volcanic gases from the Owakudani geothermal area on Hakone volcano,Japan

The chemical and isotopic compositions of volcanic gases at a borehole and a natural fumarole in the Owakudani geothermal area, Hakone volcano, Japan, have been repeatedly measured since 2001, when a seismic swarm occurred in the area. The CO₂/H₂O and CO₂/H₂S ratios were high in 2001. It increased in 2006 and again in 2008 when seismic swarms occurred beneath the geothermal area. The observed increases suggest the injection of CO₂- and SO₂-rich magmatic gas into the underlying hydrothermal reservoir, implying that the magmatic gas was episodically supplied to the hydrothermal system in 2006 and 2008. The earthquake swarms probably resulted from the injection of gas through the shallow crust accompanying the break of the sealing zone.     

Hydrochemical characteristics and salinization processes of groundwater in the shallow aquifer of Eastern Laizhou Bay,China

Groundwater salinization has become a crucial environmental problem worldwide and is considered the most widespread form of groundwater contamination in the coastal zone. In this study, a hydrochemical investigation was conducted in the eastern coastal shallow aquifer of Laizhou Bay to identify the hydrochemical characteristics and the salinity of groundwater using ionic ratios, deficit or excess of each ions, saturation indices and factor analysis. The results indicate that groundwater in the study area showed wide ranges and high standard deviations for most of hydrochemical parameters and can be classified into two hydrochemical facies, Ca²⁺‐Mg²⁺‐Cl^‐ facies and Na⁺‐Cl^‐ facies. The ionic ratio, deficit or excess of each ions and SI were applied to evaluate hydrochemical processes. The results obtained indicate that the salinization processes in the coastal zones were inverse cation exchange, dissolution of calcite and dolomite, and intensive agricultural practices. Factor analysis shows that three factors were determined (Factor 1: TDS, EC, Cl^‐, Mg²⁺, Na⁺, K⁺, Ca²⁺ and SO₄^2‐; Factor 2: HCO₃^‐ and pH; Factor 3: NO₃^‐ and pH), representing the signature of seawater intrusion in the coastal zone, weathering of water–soil/rock interaction, and nitrate contamination, respectively. Copyright © 2011 John Wiley & Sons, Ltd.     

Diffuse CO<Subscript>2</Subscript> degassing at Vesuvio,Italy

At Vesuvio, a significant fraction of the rising hydrothermal–volcanic fluids is subjected to a condensation and separation process producing a CO₂–rich gas phase, mainly expulsed through soil diffuse degassing from well defined areas called diffuse degassing structures (DDS), and a liquid phase that flows towards the outer part of the volcanic cone. A large amount of thermal energy is associated with the steam condensation process and subsequent cooling of the liquid phase. The total amount of volcanic–hydrothermal CO₂ discharged through diffuse degassing has been computed through a sequential Gaussian simulation (sGs) approach based on several hundred accumulation chamber measurements and, at the time of the survey, amounted to 151 t d^–1. The steam associated with the CO₂ output, computed assuming that the original H₂O/CO₂ ratio of hydrothermal fluids is preserved in fumarolic effluents, is 553 t d^–1, and the energy produced by the steam condensation and cooling of the liquid phase is 1.47×10¹² J d^–1 (17 MW). The location of the CO₂ and temperature anomalies show that most of the gas is discharged from the inner part of the crater and suggests that crater morphology and local stratigraphy exert strong control on CO₂ degassing and subsurface steam condensation. The amounts of gas and energy released by Vesuvio are comparable to those released by other volcanic degassing areas of the world and their estimates, through periodic surveys of soil CO₂ flux, can constitute a useful tool to monitor volcanic activity.Editorial responsibility: H. Shinohara     

A simple method for the collection and analysis of volcanic gas samples

Investigations into the chemistry of volcanic gases depend on the availability of complete and accurate analyses of volcanic exhalations. The wide variety of sampling and analysis methods hitherto used, often supplying only partial analyses of low precision, made intercomparison, and thus a systematic study of volcanic gases, difficult. With the method proposed here, complete volcanic gas samples are obtained permitting the accurate determination of all major species by standard analytical methods without the need for highly specialised ancillary equipment. The samples are collected in evacuated 300 ml pyrex flasks through titanium tubes deeply inserted into the gas vent. Two types of flask are used, a single compartment flask allowing the easy determination of the major constituents and containing 50 ml 4 N NaOH, and a double compartment flask for the separate analysis of the sulfur species and containing 25 ml 0.1 N As₂O₃ in 1 N HClO₄ in the first, and 50 ml 4 N NaOH in the second compartment. Non-absorbed gases are determined by gas chromatography, the rest by standard analytical procedures. The determination of H₂O, CO₂, SO₂, SO₂, S₂, H₂S, HCl, HF, H₂, N₂, O₂, CH₄, CO and NH₂ is described.     

Tomographic imaging of seismic velocity structure in and around the Onikobe volcanic area, northeastern Japan: implications for fluid distribution

We estimated three-dimensional P- (V_p) and S-wave velocity (V_s) and V_p/V_s structures in and around the Onikobe volcanic area, northeastern Japan, by local travel time tomography. We used travel time data from source and receiver pairs located within and outside the study area, which plays an important role in obtaining the optimum ray coverage and in elucidating the deeper structure more accurately. Detailed information on deeper structures is essential for imaging the complete volcanic system from the magmatic source zone through areas of shallow hydrothermal circulation. More than 50 000 travel time data for the P-waves and 35 000 for the S-waves were used to image the velocity structure. Our results show the following dominant features: (1) two conduits in the upper crust with low V_p and low V_s indicative of H₂O-rich fluid pathways: one lying beneath Naruko volcano, the other beneath the focal area of the 1962 Northern Miyagi earthquake (M6.5); (2) an underlying broad region in the lower crust with low V_p, low V_s and high V_p/V_s, suggestive of a zone of partial melt, from which the fluids in (1) are derived; and (3) low V_p/V_s areas near the surface of the Sanzugawa and Onikobe calderas, suggesting a diffuse vapor-saturated cap.     

CO2 and H2S concentrations in the atmosphere at the Solfatara of Pozzuoli

The CO₂ and H₂S concentration in the Solfatara atmosphere has been measured. The concentrations of both gases are higher neraby the more active areas and decrease away from them. A sharp horizontal and vertical gradient of the CO₂ content has been recognized.Such gradient is assumed to result from a diffusion of gas from the ground to the atmosphere.The total output of CO₂ has been computed based on a turbulent diffusion model. The obtained value is in good agreement with previously abserved values (Italiano et al., 1984).The feasibility of monitoring the atmosphere of Solfatara for either gas hazard and surveillance of volcanic activity has also been evaluated.     

Forecast of volcanic eruptions by chemical methods

From the magmatic emanations differentiation point of view it is possible to calculate some ratios such as F/CO₂, Cl/CO₂, SO₂/CO₂, SO₂/H₂S, H₂S/CO₂ and CO₂/N₂ in the tumarolic gases for the forecasting of volcanic activity. In order to predict the cruptions of a volcano it is needed to select several fumaroles or hot springs having different regimes of variation of the above ratios. The study of some fumaroles composition at the Asama. Mihara, Kirishima and other volcanoes in Japan showed a close connection between volcanic gas compositions and state of the volcanoes.     

Equilibrium calculations in volcanic gaseous systems

Equilibria calculations of high-temperature volcanic gases from lava lakes are carried out on the basis of best volcanic gas samples. The equilibrium gas composition at temperatures from 800° to 1400°K and pressures up to 25 kilobars (in ideal gas system) was calculated using the free energy minimization model as well as the Newton-Raphson methods. It is shown that the juvenile «magmatic gas » of basaltic magma consists of three components: H₂O, SO₂, CO₂; the water vapor being about 60%. The increase of temperature under constant pressure results in the increase of the SO₂ concentration and in the simultaneous decrease of H₂S. Under the same conditions the ratios CO/CO₂ and H₂/H₂O are found to increase. Methane cannot be a component of «magmatic gas» corresponding to the elemental composition of basaltic lava gases. The calculated values of \(P_{O_2 } \) are in good agreement with the experimental data obtained from direct measurements of \(P_{O_2 } \) in lava lakes and experiments with basaltic melts.     

Erta'ale lava lake: heat and gas transfer to the atmosphere

Data on uncontaminated samples of volcanic gases can be counted on the fingers of one hand, yet estimation of total volcanic gas flow cannot be made without such data. In this paper the flux of gas from the lava lake to the atmosphere is calculated by a heat budget based on the excess heat loss caused by combustion of H₂ and CO and by the mass rate of loss of other gases on the basis of their ratios to H₂ and CO in the unoxidized gas samples. The estimated rates of loss of H₂O, CO₂, SO₂ and HCl are consistent with the rate of loss of heat if this heat is generated by crystallization and if the initial magma contains concentrations of gas appropriate for submarine basalt from oceanic ridges. The moderate activity of permanent degassing from the two active lava ponds studied gives a lower flux than that of other volcanoes.     

S-wave shadows in the Krafla Caldera in NE-Iceland,evidence for a magma chamber in the crust

During the present tectonic activity in the volcanic rift zone in NE-Iceland it has become apparent that the attenuation of seismic waves is highly variable in the central region of the Krafla volcano. Earthquakes associated with the inflation of the volcano have been used to delineate two regions of high attenuation of S-waves within the caldera. These areas are located near the center of inflation have horizontal dimensions of 1–2 km and are interpreted as the expression of a magma chamber. The top of the chamber is constrained by hypocentral locations and ray paths to be at about 3 km depth. Small pockets of magma may exist at shallower levels. The bottom of the chamber is not well constrained, but appears to be above 7 km depth. Generally S-waves propagate without any anomalous aftenuation through laver 3 (v_p=0.5 km sec^?1) across the volcanic rift zone in NE-Iceland. The rift zone therefore does not appear to be underlain by an estensive magma chamber at crustal levels. The Krafla magma chamber is a localized feature of the Krafla central volcano.