A reconnaissance geochemical study of La Primavera geothermal area, Jalisco, Mexico

The Sierra La Primavera, a late Pleistocene rhyolitic caldera complex in Jalisco, México, contains fumaroles and large-discharge 65°C hot springs that are associated with faults related to caldera collapse and to later magma insurgence. The nearly-neutral, sodium bicarbonate, hot springs occur at low elevations at the margins of the complex, whereas the water-rich fumaroles are high and central.The Comisión Federal de Electricidad de México (CFE) has recently drilled two deep holes at the center of the Sierra (PR-1 and Pr-2) and one deep hole at the western margin. Temperatures as high as 285°C were encountered at 1160 m in PR-1, which produced fluids with 820 to 865 mg/kg chloride after flashing to one atmosphere. Nearby, PR-2 encountered temperatures to 307°C at 2000 m and yielded fluids with chloride contents fluctuating between 1100 and 1560 mg/kg after flashing. Neither of the high-temperature wells produced steam in commercial quantities. The well at the western margin of the Sierra produced fluids similar to those from the hot springs. The temperature reached a maximum of 100°C near the surface and decreased to 80°C at 2000 m.Various geothermometers (quartz conductive, Na/K, Na-K-Ca, δ¹⁸O(SO₄-H₂O) and D/H (steam-water) all yield temperatures of 170 ± 20°C when applied to the hot spring waters, suggesting that these spring waters flow from a large shallow reservoir at this temperature. Because the hot springs are much less saline than the fluids recovered in PR-1 and PR-2, the mixed fluid in the shallow reservoir can contain no more than 10–20% deep fluid. This requires that most of the heat is transferred by steam. There is probably a thin vapor-dominated zone in the central part of the Sierra, through which steam and gases are transferred to the overlying shallow reservoir. Fluids from this reservoir cool from 170°C to 65°C by conduction during the 5–7 km of lateral flow to the hot springs.     

Petrography and uplift history of the Quaternary Takidani Granodiorite: could it have hosted a supercritical (HDR) geothermal reservoir?

The Quaternary Takidani Granodiorite (Japan Alps) is analogous to the type of deep-seated (3–5 km deep) intrusive-hosted fracture network system that might support (supercritical) hot dry/wet rock (HDR/HWR) energy extraction. The I-type Takidani Granodiorite comprises: porphyritic granodiorite, porphyritic granite, biotite-hornblende granodiorite, hornblende-biotite granodiorite, biotite-hornblende granite and biotite granite facies; the intrusion has a reverse chemical zonation, characterized by >70 wt% SiO₂ at its inferred margin and <67 wt% SiO₂ at the core. Fluid inclusion evidence indicates that fractured Takidani Granodiorite at one time hosted a liquid-dominated, convective hydrothermal system, with <380°C, low-salinity reservoir fluids at hydrostatic (mesothermal) pressure conditions. ‘Healed’ microfractures also trapped >600°C, hypersaline (35 wt% NaCl_eq) fluids of magmatic origin, with inferred minimum pressures of formation being 600–750 bar, which corresponds to fluid entrapment at 2.4–3.0 km depth. Al-in-hornblende geobarometry indicates that hornblende crystallization occurred at about 1.45 Ma (7.7–9.4 km depth) in the (marginal) eastern Takidani Granodiorite, but later (at 1.25 Ma) and shallower (6.5–7.0 km) near the core of the intrusion. The average rate of uplift across the Takidani Granodiorite from the time of hornblende crystallization has been 5.1–5.9 mm/yr (although uplift was about 7.5 mm/yr prior to 1.2 Ma), which is faster than average uplift rates in the Japan Alps (3 mm/yr during the last 2 million years). A temperature–depth–time window, when the Takidani Granodiorite had potential to host an HDR system, would have been when the internal temperature of the intrusive was cooling from 500°C to 400°C. Taking into account the initial (7.5 mm/yr) rate of uplift and effects of erosion, an optimal temperature–time–depth window is proposed: for 500°C at 1.54–1.57 Ma and 5.2±0.9 km (drilling) depth; and 400°C at 1.36–1.38 Ma and 3.3±0.8 km (drilling) depth, which is within the capabilities of modern drilling technologies, and similar to measured temperature–depth profiles in other active hydrothermal systems (e.g. at Kakkonda, Japan).     

Simultaneous radio and optical observations of the mid-latitude atmospheric response to a major geomagnetic storm of 6–8 April 2000

Basic properties of the mid-latitude traveling ionospheric disturbances (TIDs) during the maximum phase of a major magnetic storm of 6–8 April 2000 are shown. Total electron content (TEC) variations were studied by using data from GPS receivers located in Russia and Central Asia. The nightglow response to this storm at mesopause and termospheric altitudes was also measured by optical instruments FENIX located at the observatory of the Institute of Solar-Terrestrial Physics (51.9°N,103.0°E), and MORTI located at the observatory of the Institute of Ionosphere (43.2°N, 77.0°E). Observations of the O (557.7 and 630.0 nm) emissions originating from atmospheric layers centered at altitudes of 90 and 250 km were carried out at Irkutsk and of the O₂(b¹∑_g⁺−X³∑_g⁻) (0-1) emission originating from an atmospheric layer centered at altitude of 94 km was carried out at Almaty. Our radio and optical measurement network observed a storm-induced solitary large-scale wave with duration of 1 h and a wave front width of no less than 5000 km, while it traveled equatorward with a velocity of 200 m/s from 62°N to 38°N geographic latitude. The TEC disturbance, basically displaying an electron content depression in the maximum of the F2 region, reveals a good correlation with growing nightglow emission, the temporal shift between the TEC and emission variation maxima being different for different altitudes. A comparison of the auroral oval parameters with dynamic spectra of TEC variations and optical 630 nm emissions in the frequency range 0.4–4 mHz (250–2500 s periods) showed that as the auroral oval expands into mid-latitudes, also does the region with a developed medium-sale and small-scale TEC structure.     

Isotope geochemistry of minerals and fluids from Newberry volcano, Oregon

Isotopic compositions were determined for hydrothermal quartz, calcite, and siderite from core samples of the Newberry 2 drill hole, Oregon. The δ¹⁵O values for these minerals decrease with increasing temperatures. The values indicate that these hydrothermal minerals precipitated in isotopic equilibrium with water currently present in the reservoirs. The δ¹⁸O values of quartz and calcite from the andesite and basalt flows (700–932 m) have isotopic values which require that the equilibrated water δ¹⁸O values increase slightly (− 11.3 to −9.2‰) with increasing measured temperatures (150–265°C). The lithic tuffs and brecciated lava flows (300–700 m) contain widespread siderite. Calculated oxygen isotopic compositions of waters in equilibrium with siderite generally increase with increasing temperatures (76–100°C). The δ¹⁸O values of siderite probably result from precipitation in water produced by mixing various amounts of the deep hydrothermal water (− 10.5 ‰) with meteoric water (− 15.5 ‰) recharged within the caldera. The δ¹³C values of calcite and siderite decrease with increasing temperatures and show that these minerals precipitated in isotopic equilibrium with CO₂ of about −8 ‰.The δ¹⁸O values of weakly altered (<5% alteration of plagioclase) whole-rock samples decrease with increasing temperatures above 100°C, indicating that exchange between water and rock is kinetically controlled. The water/rock mass ratios decrease with decreasing temperatures. The δ¹⁸O values of rocks from the bottom of Newberry 2 show about 40% isotopic exchange with the reservoir water.The calculated δ¹⁸O and δD values of bottom hole water determined from the fluid produced during the 20 hour flow test are −10.2 and −109‰, respectively. The δD value of the hydrothermal water indicates recharge from outside the caldera.     

Petrology and Fe–Ti oxide reequilibration of the 1991 Mount Unzen mixed magma

A dacitic magma (64.5 wt.% SiO₂), a mixture of phenocryst-rich rhyodacite and an aphyric mafic magma, was erupted during the recent 1991–1995 Mount Unzen eruptive cycle. The experimental and analytical results of this study reveal additional details about conditions in the premixing and postmixing magmas, and the nature of the mixing process. The preeruption rhyodacitic magma was at a temperature of 790±20°C according to Fe–Ti oxide phenocryst cores, and at a depth of 6 to 7 km (160 MPa) according to Al-in-hornblende geobarometry. The mafic magma that mixed with the rhyodacite is found as andesitic (54 to 62 wt.% SiO₂) enclaves in the erupted magma and was essentially aphyric when intruded. Phase equilibria indicate that an aphyric andesite at 160 MPa is >1030°C (H₂O-saturated) and possibly as high as 1130°C (2 wt.% H₂O). The composition of the rhyodacite which was mixed with the andesite is estimated to lie between 67 and 69 wt.% SiO₂. Using these compositions and temperatures, the temperature of the Unzen magma after mixing is estimated to be at least 850° to 870°C. The groundmass Fe–Ti oxide microphenocrysts and those in pargasite-bearing reaction zones around biotite phenocrysts both give 890±20°C temperatures; the oxide–oxide contacts give temperatures of 910±20°C. The 900±30°C postmixing temperatures are consistent with phase-equilibria experiments which show that the magma was not above 930°C at 160 MPa. Our Fe–Ti oxide reequilibration experiments suggest that the mixing of the two magmas began within a few weeks of the eruption, which is a shorter time than is calculated using available diffusion data. There is also evidence that some mixing took place much closer to the time of extrusion based on the presence of unrimmed biotite phenocrysts in the magma.     

Gas geochemistry of the Valles caldera region, New Mexico and comparisons with gases at Yellowstone, Long Valley and other geothermal systems

Noncondensible gases from hot springs, fumaroles, and deep wells within the Valles caldera geothermal system (210–300°C) consist of roughly 98.5 mol% CO₂, 0.5 mol% H₂S, and 1 mol% other components. ³He/⁴He ratios indicate a deep magmatic source (R/R_a up to 6) whereas δ¹³C–CO₂ values (−3 to −5‰) do not discriminate between a mantle/magmatic source and a source from subjacent, hydrothermally altered Paleozoic carbonate rocks. Regional gases from sites within a 50-km radius beyond Valles caldera are relatively enriched in CO₂ and He, but depleted in H₂S compared to Valles gases. Regional gases have R/R_a values ≤1.2 due to more interaction with the crust and/or less contribution from the mantle. Carbon sources for regional CO₂ are varied. During 1982–1998, repeat analyses of gases from intracaldera sites at Sulphur Springs showed relatively constant CH₄, H₂, and H₂S contents. The only exception was gas from Footbath Spring (1987–1993), which experienced increases in these three components during drilling and testing of scientific wells VC-2a and VC-2b. Present-day Valles gases contain substantially less N₂ than fluid inclusion gases trapped in deep, early-stage, post-caldera vein minerals. This suggests that the long-lived Valles hydrothermal system (ca. 1 Myr) has depleted subsurface Paleozoic sedimentary rocks of nitrogen. When compared with gases from many other geothermal systems, Valles caldera gases are relatively enriched in He but depleted in CH₄, N₂ and Ar. In this respect, Valles gases resemble end-member hydrothermal and magmatic gases discharged at hot spots (Galapagos, Kilauea, and Yellowstone).     

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.     

Geochemistry and isotopes of fluids from sulphur springs, Valles Caldera, New Mexico

Detailed geochemistry supported by geologic mapping has been used to investigate Sulphur Springs, an acid-sulfate hot spring system that issues from the western flank of the resurgent dome inside Valles Caldera. The most intense activity occurs at the intersection of faults offsetting caldera-fill deposits and post-caldera rhyolites. Three geothermal wells in the area have encountered pressures <1 MPa and temperatures of 200°C at depths of 600 to 1000 m. Hot spring and fumarole fluids may discharge at boiling temperatures with pH 1.0 and SO₄ 8000 mg/l. These conditions cause argillic alterations throughout a large area.Non-condensible gases consist of roughly 99% CO₂ with minor amounts of H₂S, H₂, and CH₄. Empirical gas geothermometry suggests a deep reservoir temperature of 215 to 280°C. Comparison of ¹³C and ¹⁸O between CaCO₃ from well cuttings and CO₂ from fumarole steam indicates a fractionation temperature between 200 and 300°C by decarbonation of hydrothermally altered Paleozoic limestone and vein calcite in the reservoir rocks. Tritium concentrations obtained from steam condensed in a mudpot and deep reservoir fluids (Baca #13, 278°C) are 2.1 and 1.0 T.U. respectively, suggesting the steam originates from a reservoir whose water is mostly >50 yrs old. Deuterium contents of fumarole steam, deep reservoir fluid, and local meteoric water are practically identical even though ¹⁸O contents range through 4‰, thus, precipitation on the resurgent dome of the caldera could recharge the hydrothermal system by slow percolation. From analysis of D and ¹⁸O values between fumarol steam and deep reservoir fluid, steam reaches the surface either (1) by vaporizing relatively shallow groundwater at 200°C or (2) by means of a two-stage boiling process through an intermediate level reservoir at roughly 200°C.Although many characteristics of known vapor-dominated geothermal systems are found at Sulphur Springs, fundamental differences exist in temperature and pressure of our postulated vapor-zone. We propose that the reservoir beneath Sulphur Springs is too small or too poorly confined to sustain a “true” vapor-dominated system and that the Sulphur Springs system may be a “dying” vapor-dominated system that has practically boiled itself dry.     

Hydrothermal silica chimney fields in the Galapagos Spreading Center at 86°W

Silica chimneys were discovered in 1985 at 86°W in the rift valley of the Galapagos Spreading Center at 2600 m depth (“Cauliflower Garden”). The inactive chimneys lack any sulfides and consist almost entirely of amorphous silica (up to 96 wt.% SiO₂, opal-A); Fe and Mn oxides are minor constituents. Oxygen isotope data show that formation of the silica chimneys took place at temperatures between 32°C (+29.9‰ δ¹⁸O) and 42°C (+27.8‰ δ¹⁸O).Th/Udating reveals a maximum age of 1440 ± 300y. Amorphous silica solubility relations indicate that the silica chimneys were formed by conductive cooling of pure hydrothermal fluids or by conductive cooling of a fluid/seawater mixture. Assuming equilibrium with quartz at 500 bars, initial fluid temperatures of more than 175°C (i.e., a concentration of > 182 ppm SiO₂) were required to achieve sufficient supersaturation for the deposition of amorphous silica at 40°C and 260 bars. If the silica chimneys originate from the same or a similar fluid as higher-temperature ( < 300°C) sulfide-silica precipitates found nearby (i.e., 2.5 km away), then subsurface deposition of sulfides may have occurred.     

Hydrothermal vent waters at 13°N on the East Pacific Rise: isotopic composition and gas concentration

Gas concentrations and isotopic compositions of water have been measured in hydrothermal waters from 13°N on the East Pacific Rise. In the most Mg-depleted samples ( 5 × 10⁻³ moles/kg) the gas concentrations are: 3–4.5 × 10⁻⁵ cm³ STP/kg helium, 0.62–1.24 cm³ STP/kg CH₄, 10.80–16.71 × 10⁻³ moles/kg CO₂. The samples contain large quantities (95–126 cm³/kg) of H₂ and some carbon monoxide (0.26–0.36 cm³/kg) which result from reaction with the titanium sampling bottles. δ¹³C in methane and CO₂ (−16.6 to −19.5 and −4.1 to −5.5 respectively) indicate temperatures between 475 and 550°C, whereas δ¹³C_CO is compatible with formation by reduction of CO₂ on Ti at 350°C close to the sampling temperature.³He/⁴He are very homogeneous at (7.5 ± 0.1)R_A(³He/⁴He = 1.0 × 10⁻⁵) and very similar to already published data as well as CH₄/³He ratios between 1.4 and 2.1 × 10⁶.¹⁸O and D in water show enrichments from 0.39 to 0.69‰ and from 0.62 to 1.49‰ respectively. These values correspond to W/R ratios of 0.4–7. The distinct¹⁸O enrichments indicate that the isotopic composition of the oceans is not completely buffered by the hydrothermal circulations. The³He-enthalpy relationship is discussed in terms of both hydrothermal heat flux and³He mantle flux.     

Geochemical investigations of submarine volcanic exhalations to the east of Panarea, Aeolian Islands, Italy

Results are presented on scubadiving investigations carried out on thermal manifestations in the area of Panarea (Aeolian Islands). The area investigated falls inside a caldera which extends from the main island to the group of islets located to the northeast. The distribution of the gaseous manifestations is regulated by the NE-SW, NW-SE and N-S regional tectonic directrices, through which the more recent basic magma intruded, giving rise to dikes and pillow lavas. f_O2-temperature relation of the gases sampled in the investigated area was calculated to be: logf_O2 = 11−24,593/T which indicates that a buffering mechanism acted on the gases as they cooled down during their ascent. The high ³He/⁴He ratio (6 × 10⁻⁶) and the δ¹³C = −3.2%. (PDB), suggest the presence of a magmatic component in the gas feeding the investigated manifestations. The above relations and the almost constant high He/N₂ ratio suggest that all the fumaroles are fed by the same deep hot fluids. On the basis of both the chemical characters of the fluids and the geothermo-barometric data, a deep geothermal body, having a temperature of about 240°C, is recognized. Two other shallower thermal aquifers, with a temperature of 170–210°C, are identified. A circulation pattern of the geothermal fluids is also proposed. On the basis of calculations regarding the convective energy released by the geothermal system of Panarea, and the magmatic mass responsible for the positive gravimetric anomaly of the area, it was estimated that the last volcanic activity took place less then 10,000 years ago.     

The behaviour of metals and sulphur during the formation of hydrothermal mercury–antimony–arsenic mineralization, Uzon caldera, Kamchatka, Russia

Uzon caldera, located in the eastern volcanic belt of the Kamchatka peninsula, is a complicated structure of Middle Pleistocene age. The composition of the co-existing solid and fluid phases, temperature and pH were determined with the aim of establishing the distribution of sulphur species, As, Sb and the main ore-forming metals. In the solid samples, the following sulphur-bearing minerals were identified: pyrite, realgar, orpiment, alacranite (As₈S₉), uzonite (As₄S₅), amorphous As-sulphide, stibnite, cinnabar and native sulphur. The following sulphur-bearing species H₂S, H₂S₂+S₅²⁻(aq)(aqueous polysulphanes), S⁰(aq), SO₃²⁻(aq), S₂O₃²⁻, SO₄²⁻ and total concentration of sulphur were determined in solutions. Eh, pH and H₂S concentration were measured potentiometrically in situ. Zero-valent sulphur (S⁰(aq)+H₂S₂+S₅²⁻(aq)) predominates in Uzon solutions. The pair H₂S–S_colloidal is Eh-determining in Uzon solutions up to 75–85°C. A quantitative thermodynamic model of the mineral deposition process at Uzon was constructed using the collected data. It was obtained that the composition of the hydrothermal solution and the precipitation of Sb–As–Hg species can be described using two only main factors: the initial composition of fluid and the temperature variation.     

Water–Rock interactions in the basement beneath Long Valley Caldera: an oxygen isotope study of the Long Valley Exploratory Well drill cores

The Long Valley Exploratory Well, at the center of the Resurgent Dome of Long Valley caldera, penetrated pre-caldera basement rocks at a depth of 2101.72–2313.0 m, beneath the caldera-forming Bishop Tuff and post-caldera Early Rhyolite. The basement rocks contain prominent quartzites, with ubiquitous milky white quartz veins (with minor calcite and pyrite) and fractures of varied orientation and geometry. The other members of the basement sequence are very fine-grained quartz-rich graphitic pelites with calcite veins, spotted hornfels, and shallow intrusive rocks. Previous studies established the presence of a post-caldera, paleohydrothermal system (500–100 ka) to a depth of 2000 m that affected the Bishop Tuff and a recent (40 ka to present) hydrothermal system at shallow depth (<1 km). The deeper extent of these hydrothermal activities is established in this paper by a detailed oxygen isotope analysis of the drill core samples. 238 analyses of δ¹⁸O in 50 quartz veins within the 163.57 m depth interval of basement rocks reveal extreme heterogeneity in δ¹⁸O values (8–19.5‰). Majorities of the 84 bulk analyses of quartzites show variation of δ¹⁸O within a narrow range of 14–16‰. However, certain samples of these quartzites near the contacts with veins and fractures exhibit sharp drops in δ¹⁸O. The interbedded pelitic rocks and spotted hornfels have whole-rock δ¹⁸O ranging from 2.2 to 11.8‰. Clear, euhedral vuggy quartz that partially fills earlier open fractures in both the quartzites and quartz veins, has distinctive δ¹⁸O, ranging between −3.2 and +8.4‰. Low values of δ¹⁸O are also found in the hydrothermal minerals and whole rocks adjacent to the thin veins, clearly indicating infiltration of meteoric water. Three distinct observed patterns of fractionation in δ¹⁸O between veins and host quartzites are analyzed with the principles of mass balance, equilibrium oxygen isotope fractionation in closed system, and kinetically controlled oxygen isotope exchange in an open system. This analysis suggests that the early quartz veins formed due to a magmatic-hydrothermal activity with no influx of external water once the system comprising the sedimentary envelope and a magmatic-hydrothermal fluid phase became closed. Two-stage isotopic exchange processes caused fractionation in the δ values that originally formed arrays with slope 1 in a δ_{vein quartz}–δ_{host quartzite} space. Another array in the same space, with near zero slope was also formed due to variation in temperature, initial isotopic compositions of the quartzite sequence and the fluid phase. Variation in temperature was mostly in the range of 300–400°C giving Δ (=δ_{vein quartz}–δ_{host quartzite})≈−2.8 to +2.8. The δ¹⁸O of the fluid could range from −5 to +10; however a narrower range of +5 to +10 can explain the data. This episode of hydrothermal activity could take place either as a single pulse or in multiple pulses but each as a closed system. A later, fracture-controlled, meteoric water (δ¹⁸O−0.46 to −12.13) flow and interaction (at 250°C) is interpreted from the analysis of δ¹⁸O values of the coexisting quartz and calcite pairs and existence of markedly ¹⁸O-depleted pelitic horizons interbedded with ¹⁸O-enriched quartzite layers. Thus, the interpreted earlier magmatic-hydrothermal activity was overprinted by a later meteoric-hydrothermal activity that resulted in steep arrays of δ¹⁸O values in the δ_{vein quartz}–δ_{host quartzite} space. Calculations show that the likely life span of the post-caldera, hydrothermal activity in the depth range of 2.1–2.3 km beneath Long Valley was 0.08–0.12 Ma. Diffusive ±advective transport of oxygen isotopes from fracture-channelized meteoric water to nearly impermeable wall rocks caused a lowering of δ¹⁸O values in the quartz over short distances and in calcites over greater distances. Thus, the hydrothermal activity appears pervasive even though the meteoric water flow was primarily controlled by fractures.     

Hydrogeochemistry of the Simav geothermal field, western Anatolia, Turkey

Thermal waters hosted by Menderes metamorphic rocks emerge along fault lineaments in the Simav geothermal area. Thermal springs and drilled wells are located in the Eynal, Çitgöl and Na a locations, which are part of the Simav geothermal field. Studies were carried out to obtain the main chemical and physical characteristics of thermal waters. These waters are used for heating of residences and greenhouses and for balneological purposes. Bottom temperatures of the drilled wells reach 163°C with total dissolved solids around 2225 mg/kg. Surface temperatures of thermal springs vary between 51°C and 90°C. All the thermal waters belong to Na–HCO₃–SO₄ facies. The cold groundwaters are Ca–Mg–HCO₃ type. Dissolution of host rock and ion-exchange reactions in the reservoir of the geothermal system shift the Ca–Mg–HCO₃ type cold groundwaters to the Na–HCO₃–SO₄ type thermal waters. Thermal waters are oversaturated at discharge temperatures for aragonite, calcite, quartz, chalcedony, magnesite and dolomite minerals giving rise to a carbonate-rich scale. Gypsum and anhydrite minerals are undersaturated with all of the thermal waters. Boiling during ascent of the thermal fluids produces steam and liquid waters resulting in an increase of the concentrations of the constituents in discharge waters. Steam fraction, y, of the thermal waters of which temperatures are above 100°C is between 0.075 and 0.119. Reservoir pH is much lower than pH measured in the liquid phase separated at atmospheric conditions, since the latter experienced heavy loss of acid gases, mainly CO₂. Assessment of the various empirical chemical geothermometers and geochemical modelling suggest that reservoir temperatures vary between 175°C and 200°C.     

Petrology of the Easter microplate region in the South Pacific

Submersible investigations along the East Rift segments, the Pito Deep and the Terevaka transform fault of the Easter microplate eastern boundary, and on a thrust-fault area of the Nazca Plate collected a variety of basalts and dolerites. The volcanics consist essentially of depleted (N-MORB), transitional (T-MORB) and enriched (E-MORB) basalts with low (0.01−0.1, < 0.7), intermediate (0.12–0.25, 0.7–1.2) and high (> 0.25, > 1.2–2) K/Ti and(La/Sm)_N ratios, respectively. The Fe-Ti-rich ferrobasalt encountered among the N-MORBs are found on the Pito Deep Central volcano, on the Terevaka intra-transform ridge, on the ancient (< 2.5 Ma) Easter microplate (called EMP, comprising the East Rift Inner pseudofaults and Pito Deep west walls) and on thrust-fault crusts. The most enriched (T- and E-MORB) volcanics occur along the East Rift at 25 °50′–27 °S (called 26 °S East Rift) and on the Pito seamount located near the tip of the East Rift at 23 °00′–23 °40′S (called 23 °S East Rift). The diversity in incompatible element ratios of the basalts in relation to their structural setting suggests that the volcanics are derived from a similar heterogenous mantle which underwent variable degrees of partial melting and magma mixing. In addition the Pito seamount volcanics have undergone less crystal fractionation (< 20%) than the lavas from the other Easter microplate structures (up to 35–45%). The tectonic segmentation of the East Rift observed between 23 and 27 °S corresponds to petrological discontinuities related to Mg# variations and mantle melting conditions. The highest Mg# (> 61) are found on topographic highs (2000–2300 m) and lower values (Mg# < 56) at the extremities of the East Rift segments (2500–5600 m depths). The deepest area (5600 m) along the East Rift is located at 23 °S and coincides with a Central volcano constructed on the floor of the Pito Deep. Three major compositional variabilities of the volcanics are observed along the East Rift segments studied: (1) the 26 °S East Rift segment where the volcanics have intermediate Na₈ (2.5–2.8%) and Fe₈ (8.5–11%) contents; (2) the 23 °S East Rift segment (comprising Pito seamount and Pito Deep Central volcano) which shows the highest (2.9–3.4%) values of Na₈ and a low (8–9%) Fe₈ content; and (3) the 25 °S (at 24 °50′–26 °10′S) and the 24 °S (at 24 °10′–25 °S) East Rift segments where most of the volcanics have low to intermediate Na₈ (2.6–2.0%) and a high range of Fe₈ (9–13%) contents. When modeling mantle melting conditions, we observed a relative increase in the extent of partial melting and decreasing melting pressure. These localized trends are in agreement with a 3-D type diapiric upwelling in the sense postulated by Niu and Batiza (1993). Diapiric mantle upwelling and melting localized underneath the 26, 25 and 23 °S (Pito seamount and Central volcano) East Rift segments are responsable for the differences observed in the volcanics. The extent of partial melting varies from 14 to 19% in the lithosphere between 18 and 40 km deep as inferred from the calculated initial (P_o=16kbar) and final melting (P_f=7kbar) pressures along the various East Rift segments. The lowest range of partial melting (14–16%) is confined to the volcanics from 23 °S East Rift segment including the Pito seamount and the Central volcano. The Thrust-fault area, and the Terevaka intra-transform show comparable mantle melting regimes to the 25 and 26 °S East Rift segments. The older lithosphere of the EMP interior is believed to have been the site of high partial melting (17–20%) confined to the deeper melting area (29–50 km). This increase in melting with increasing pressure is similar to the conditions encountered underneath the South East Pacific Rise (13–20 °S).     

Depth distribution of stresses in the Hokkaido Wadati-Benioff zone as deduced by inversion of earthquake focal mechanisms

This study is based on the detailed geometry of the Hokkaido Wadati-Benioff zone and the paleosubduction zone as delineated by Hanus and Vanek (1984). The used data includes 217 CMT Harvard solutions for earthquakes, which belong to the Wadati-Benioff zone and 13 for the paleosubduction zone. The inverse technique by Gephart and Forsyth (1984) was incorporated for determining the best fit principal stress directions σ₁, σ₂, σ₃ and the ratio (R=σ₂−σ₁/σ₃−σ₁) for 20 km depth intervals in the Wadati-Benioff zone and for the paleosubduction zone considered as a single body. In almost all the considered depth layers, the maximum compressive stress σ₁ is normal to the strike of the slab and dips less than 25°, indicating the NW-SE convergence between the Pacific and Eurasian lithospheric plates. Exceptions are in the depth layer 81–120 km, the paleosubduction zone with steeply dipping along-strike σ₁, and the lower part of the subduction zone (161–220 km) where σ₁ is almost horizontal and of E trend. The minimum compressive stress σ₃ is mostly along-strike and of a different dip with the exception of the 21–60 km layer wher they are down-dipping. The results obtained for the depth ranges 0–20 km, 81–100 km, 121–160 km, and the paleosubduction zone indicate heterogeneous stress fields. These results show that the slab pull and the mantle resistance, acting on the slab edge, are not the main forces which control the contemporary plate tectonics in the Hokkaido region. Along-strike compression at depths 81–120 km and along-strike extension at 0–20 and 61–220 km are involved in the slab dynamics. These can be related to horizontal bending of the subducting Pacific plate.     

Phase transformations in a harzburgite composition to 26 GPa: implications for dynamical behaviour of the subducting slab

The mineralogy adopted by a depleted harzburgite composition has been studied over the pressure interval 5–26 GPa at temperatures of 1300–1400°C. The pyroxene-garnet component of the harzburgite composition (harzburgite minus 82 wt.% olivine) transforms to majorite garnet by 18–19 GPa, and further disproportionates to the assemblage of garnet + stishovite + Mg₂SiO₄ spinel above 20 GPa. At still higher pressures, first ilmenite (22–24 GPa) and then perovskite MgSiO₃ (24–26 GPa) are found to coexist with garnet. Garnet disappears at 26 GPa and almost complete transition to perovskite is achieved at this pressure. The mineral proportions and density profiles in the subducting oceanic lithosphere, modelled by a combination of 80% harzburgite + 20% primitive MORB compositions are calculated as a function of depth under conditions isothermal with surrounding pyrolite mantle, and also for a temperature distribution in which the slab is substantially cooler than surrounding mantle to below 700 km. Under isothermal conditions, the slab has a density similar to surrounding mantle to a depth of 600 km. However, between 600 and 700 km, the slab is up to 0.08 g/cm³ denser than surrounding mantle. This is caused primarily by the higher alumina content in pyrolite as compared to harzburgite, which causes the transition to perovskite in pyrolite to occur at substantially higher pressures than in harzburgite. The presence of alumina also smears out the garnet-perovskite transition in pyrolite over a depth interval of 50 km, whereas this transformation is much sharper in the harzburgite composition. Calculations based on the observed phase equilibria also show that a subducted cool slab remains much denser (by 0.1–0.3 g/cm³) than surrounding mantle to a depth of 700 km but possesses a density similar to surrounding mantle below this depth. These results have important implications for the dynamical behaviour of slabs possessing different thermal regimes when they encounter the 670 km discontinuity and also for the nature of this discontinuity.     

Tectonic assembly of the Brevard-Chauga belt, South Carolina: Fluid inclusion evidence from Appalachian Deep Core Site Investigation Hole 2 (ADCOH-2)

Appalachian Deep Core Hole 2 (ADCOH-2) penetrated part of one of the most persistent and important tectonostratigraphic belts in the southern Appalachians—the Brevard-Chauga belt in South Carolina. The Brevard-Chauga belt is a subdivision of the Inner Piedmont and it includes the Brevard fault zone. The 307 m core contains four imbricated slices of Early Ordovician Henderson Gneiss and metasedimentary rocks of the Chauga River Formation. Aqueous (NaCl–CaCl₂) inclusions and CO₂–CH₄-rich inclusions present in syntectonic quartz veins in the metasedimentary units, together with garnet-biotite geothermometry, provide information on the P-T conditions during uplift. Garnet-biotite geothermometry in the Brevard metasiltstone indicates a crystallization temperature of 466±52 °C, which together with published ⁴⁰Ar/³⁹Ar hornblende data from the Chauga belt, are interpreted as a Neoacadian (late Devonian) garnet crystallization age. High-density CO₂-rich fluid inclusion isochores indicate a pressure of 4.5 kbar at 466±52 °C at this time. A Rb–Sr muscovite model age of 302 Ma in retrograde mylonitic Henderson Gneiss is interpreted as an Alleghanian recrystallization age. Fluid inclusions record a 2.5 kbar decompression event at this time, consistent with thrust assembly of the tectonostratigraphic units in the core.     

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.     

Seasonal variations in pCO2 and its controlling factors in surface seawater of the northern East China Sea

Surface partial pressure of CO₂ (pCO₂), temperature, salinity, nutrients, and chlorophyll a were measured in the East China Sea (ECS; 31°30′–34°00′N to 124°00′–127°30′E) in August 2003 (summer), May 2004 (spring), October 2004 (early fall), and November 2005 (fall). The warm and saline Tsushima Warm Current was observed in the eastern part of the survey area during four cruises, and relatively low salinity waters due to outflow from the Changjiang (Yangtze River) were observed over the western part of the survey area. Surface pCO₂ ranged from 236 to 445 μatm in spring and summer, and from 326 to 517 μatm in fall. Large pCO₂ (values >400 μatm) occurred in the western part of the study area in spring and fall, and in the eastern part in summer. A positive linear correlation existed between surface pCO₂ and temperature in the eastern part of the study area, where the Tsushima Warm Current dominates; this correlation suggests that temperature is the major factor controlling surface pCO₂ distribution in that area. In the western part of the study area, however, the main controlling factor is different and seasonally complex. There is large transport in this region of Changjiang Diluted Water in summer, causing low salinity and low pCO₂ values. The relationship between surface pCO₂ and water stability suggests that the amount of mixing and/or upwelling of CO₂-rich water might be the important process controlling surface pCO₂ levels during spring and fall in this shallow region. Sea–air CO₂ flux, based on the application of a Wanninkhof [1992. Relationship between wind speed and gas exchange over the ocean. Journal of Geophysical Research 97, 7373–7382] formula for gas transfer velocity and a set of monthly averaged satellite wind data, were −5.04±1.59, −2.52±1.81, 1.71±2.87, and 0.39±0.18 mmol m⁻² d⁻¹ in spring, summer, early fall, and fall, respectively, in the northern ECS. The ocean in this study area is therefore a carbon sink in spring and summer, but a weak source or in equilibrium with the atmosphere in fall. If the winter flux value is assumed to have been the mean of autumnal and vernal values, then the northern ECS absorbs about 0.013 Pg C annually. That result suggests that the northern ECS is a net sink for atmospheric CO₂, a result consistent with previous studies.