Aqueous sulfur speciation possibly linked to sublimnic volcanic gas-water interaction during a quiescent period at Yugama crater lake,Kusatsu–Shirane volcano,Central Japan

After the phreatic eruption in 1982–83, volcanic activities at Kusatsu–Shirane volcano had been decreasing and reached a minimum in 1990, had turned to a temporal rise in activity up to 1994 and then decreased again at least up to 1997. During this low-activity period we observed a relatively short (≤ 1 y) cyclic variation in polythionates (PT) in the Yugama lake water. Spectral power density analysis of the PT time-series by an autoregressive (maximum entropy spectral estimation, MESE) method indicates that the major frequency in the PT variations is 1.0 y^− 1 and the minor is 2–3 y^− 1 (1.0 and 0.3–0.5 y in periodicity, respectively). Annual variations in the lake temperature are ruled out for explaining these periodicities. We attribute these cyclic variations to a cyclic magnification-reduction in meteoric-water injection into a hydrothermal regime where volcanic gases from cooling magma bodies at depth and cooler oxidized groundwater come into contact with each other. This interaction may result in a periodical change in the composition and flux of SO₂ and H₂S gases being discharged into the lake and forming PT. From a phase deviation (2–3 months) in the cycles between the annual precipitation, including snowmelt, and the PT time-series, we estimated the maximal depth of a hydrothermal reservoir beneath the lake assuming a vertical hydraulic conductivity (5 × 10^− 3 cm/s) of the volcanic detritus around the summit hydrothermal system. Chloride in the lake water reached a maximum 1.5 years faster than PT. This is most likely due to a gradual elevation of the potentiometric front of a concentrated sublimnic solution in the hydrothermal reservoir. Variations of dissolved SO₂ and H₂S in the lake water were not consistent with those of the fumarolic gases on the north flank of the volcano. This fact together with additional observations strongly suggests that these fumaroles may have the same origin but are chemically modified by a subsurface aquifer. The PT monitoring at active crater lakes during a quiescent period can provide insight into the annual expansions and reductions of a volcano-hosted hydrothermal reservoir.     

Ground-based thermal imaging of lava lakes at Erebus volcano,Antarctica

Mount Erebus, a large intraplate stratovolcano dominating Ross Island, Antarctica, hosts the world's only active phonolite lava lakes. The main manifestation of activity at Erebus volcano in December 2004 was as the presence of two convecting lava lakes within an inner crater. The long-lived Ray Lake, ~ 1400 m² in area, was the site of up to 10 small Strombolian eruptions per day. A new but short-lived, ~ 1000–1200 m² lake formed at Werner vent in December 2004 sourced by lava flowing from a crater formed in 1993 by a phreatic eruption. We measured the radiative heat flux from the two lakes in December 2004 using a compact infrared (IR) imaging camera. Daily thermal IR surveys from the Main Crater rim provide images of the lava lake surface temperatures and identify sites of upwelling and downwelling. The radiative heat outputs calculated for the Ray and Werner Lakes are 30–35 MW and 20 MW, respectively. We estimate that the magma flux needed to sustain the combined heat loss is ~ 250–710 kg s^− 1, that the minimum volume of the magma reservoir is 2 km³, and that the radius of the conduit feeding the Ray lake is ~ 2 m.     

Hydrochemical dynamics of the “lake–spring” system in the crater of El Chichón volcano (Chiapas,Mexico)

El Chichón volcano (Chiapas, Mexico) erupted violently in March–April 1982, breaching through the former volcano–hydrothermal system. Since then, the 1982 crater has hosted a shallow (1–3.3 m, acidic (pH ∼ 2.2) and warm (∼ 30 °C) crater lake with a strongly varying chemistry (Cl/SO₄ = 0–79 molar ratio). The changes in crater lake chemistry and volume are not systematically related to the seasonal variation of rainfall, but rather to the activity of near-neutral geyser-like springs in the crater (Soap Pool). These Soap Pool springs are the only sources of Cl for the lake. Their geyser-like behaviour with a long-term (months to years) periodicity is due to a specific geometry of the shallow boiling aquifer beneath the lake, which is the remnant of the 1983 Cl-rich (24,000 mg/l) crater lake water. The Soap Pool springs decreased in Cl content over time. The zero-time extrapolation (1982, year of the eruption) approaches the Cl content in the initial crater lake, meanwhile the extrapolation towards the future indicates a zero-Cl content by 2009 ± 1. This particular situation offers the opportunity to calculate mass balance and Cl budget to quantify the lake–spring system in the El Chichón crater. These calculations show that the water balance without the input of SP springs is negative, implying that the lake should disappear during the dry season. The isotopic composition of lake waters (δD and δ¹⁸O) coincide with this crater lake-SP dynamics, reflecting evaporation processes and mixing with SP geyser and meteoric water. Future dome growth, not observed yet in the post-1982 El Chichón crater, may be anticipated by changes in lake chemistry and dynamics.     

Long term AVHRR observations of surface radiative flux from El Chichón crater lake (1996–2006)

It has been shown that due to the small surface of crater lakes, temperature surveillance is a problem using meteorological satellites. This is particularly true for El Chichón surface lake because it's about one tenth of an AVHRR pixel at nadir. In order to guarantee at least one unmixed pixel in AVHRR data, it is necessary to use only AVHRR data from NOAA satellite passes as close as possible to the nadir for the period 1996–2006, therefore AVHRR data of El Chichón's crater lake were only used it they were cloudless and had scan angles close to nadir. The analysis of the time series data shows that lake surface temperature had annual maximum values (> 35 °C) during 1996 and 1997 then surface temperature decay with a negative exponential trend reaching a steady state of about 30 °C in the last years (2004–2006). A seasonal temperature variation between the dry (December to May) and the wet (June to November) seasons is also observed. Differences between nocturnal and midday temperatures indicate the influence of lake energy emission (including reflectance) at midday under a strong short-wave solar radiation. Water surface radiative flux under these conditions reaches an average of 77.8 W m^− 2 and a maximum of 187.1 W m^− 2. Whereas nocturnal heat output from El Chichón crater lake has an average surface radiative flux of 20.4 W m^− 2 and a maximum of 74.3 W m^− 2.     

Origin and evolution of two contrasting thermal groundwaters (CO2-rich and alkaline) in the Jungwon area,South Korea: Hydrochemical and isotopic evidence

In the Jungwon area, South Korea, two contrasting types of deep thermal groundwater (around 20–33 °C) occur together in granite. Compared to shallow groundwater and surface water, thermal groundwaters have significantly lower δ¹⁸O and δD values (> 1‰ lower in δ¹⁸O) and negligible tritium content (mostly < 2 TU), suggesting a relatively high age of these waters (at least pre-thermonuclear period) and relatively long subsurface circulation. However, the hydrochemical evolution yielded two distinct water types. CO₂-rich water (P_CO2 = 0.1 to 2 atm) is characterized by lower pH (5.7–6.4) and higher TDS content (up to 3300 mg/L), whereas alkaline water (P_CO2 = 10^− 4.1–10^− 4.6 atm) has higher pH (9.1–9.5) and lower TDS (< 254 mg/L). Carbon isotope data indicate that the CO₂-rich water is influenced by a local supply of deep CO₂ (potentially, magmatic), which enhanced dissolution of silicate minerals in surrounding rocks and resulted in elevated concentrations of Ca²⁺, Na⁺, Mg²⁺, K⁺, HCO₃⁻ and silica under lower pH conditions. In contrast, the evolution of the alkaline water was characterized by a lesser degree of water–rock (granite) interaction under the negligible inflow of CO₂. The application of chemical thermometers indicates that the alkaline water represents partially equilibrated waters coming from a geothermal reservoir with a temperature of about 40 °C, while the immature characteristics of the CO₂-rich water resulted from the input of CO₂ in Na–HCO₃ waters and subsequent rock leaching.     

Methanogenesis in the sediment of the acidic Lake Caviahue in Argentina

The biogeochemistry of methane in the sediments of Lake Caviahue was examined by geochemical analysis, microbial activity assays and isotopic analysis. The pH in the water column was 2.6 and increased up to a pH of 6 in the deeper sediment pore waters. The carbon isotope composition of CH₄ was between − 65 and − 70‰ which is indicative for the biological origin of the methane. The enrichment factor ε increased from − 46‰ in the upper sediment column to more than − 80 in the deeper sediment section suggesting a transition from acetoclastic methanogenesis to CO₂ reduction with depth. In the most acidic surface layer of the sediment (pH < 4) methanogenesis is inhibited as suggested by a linear CH₄ concentration profile, activity assays and MPN analysis. The CH₄ activity assays and the CH₄ profile indicate that methanogenesis in the sediment of Lake Caviahue was active below 40 cm depth. At that depth the pH was above 4 and sulfate reduction was sulfate limited. Methane was diffusing with a flux of 0.9 mmol m^− 2 d^− 1 to the sediment surface where it was probably oxidized. Methanogenesis contributed little to the sediments carbon budget and had no significant impact on lake water quality. The high biomass content of the sediment, which was probably caused by the last eruption of Copahue Volcano, supported high rates of sulfate reduction which probably raised the pH and created favorable conditions for methanogens in deeper sediment layers.     

Remarkable geochemical changes and degassing at Voui crater lake,Ambae volcano,Vanuatu

Ambae (also known as Aoba), is a 38 × 16 km² lozenge-shaped island volcano with a coastal population of around 10 000. At the summit of the volcano is lake Voui — one of the largest active crater lakes worldwide, with 40 × 10⁶ m³ of acidic water perched 1400 m a.s.l. After more than 300 years of dormancy, Ambae volcano reawakened with phreatic eruptions through Voui in 1995, and culminating in a series of surtseyan eruptions in 2005, followed by a rapid and spectacular colour change of the lake from light blue to red in 2006. Integrating lake water chemistry with new measurements of SO₂ emissions from the volcano during the 2005–2006 eruptive period helps to explain the unusual and spectacular volcanic activity of Ambae — initially, a degassed magma approached the lake bed and triggered the surtseyan eruption. Depressurization of the conduit facilitated ascent of volatile-rich magma from the deeper plumbing system. The construction of a cone during eruption and the high degassing destabilised the equilibrium of lake stratification leading to a limnic event and subsequently the spectacular colour change.     

Chemical composition of fumarolic gases and spring discharges from El Chichòn volcano, Mexico: causes and implications of the changes detected over the period 1998–2000

Since the March–April 1982 eruption of El Chichòn volcano, intense hydrothermal activity has characterised the 1-km-wide summit crater. This mainly consists of mud and boiling pools, fumaroles, which are mainly located in the northwestern bank of the crater lake. During the period 1998–2000, hot springs and fumaroles discharging inside the crater and from the southeastern outer flank (Agua Caliente) were collected for chemical analyses. The observed chemical fluctuations suggest that the physico-chemical boundary conditions regulating the thermodynamic equilibria of the deep rock/fluid interactions have changed with time. The chemical composition of the lake water, characterised in the period 1983–1997 by high Na⁺, Cl⁻, Ca²⁺ and SO₄²⁻ contents, experienced a dramatic change in 1998–1999, turning from a Na⁺–Cl⁻- to a Ca²⁺–SO₄²⁻-rich composition. In June 2000, a relatively sharp increase in Na⁺ and Cl⁻ contents was observed. At the same time, SO₂/H₂S ratios and H₂ and CO contents in most gas discharges increased with respect to the previous two years of observations, suggesting either a new input of deep-seated fluids or local variations of the more surficial hydrothermal system. Migration of gas manifestations, enhanced number of emission spots and variations in both gas discharge flux and outlet temperatures of the main fluid manifestations were also recorded. The magmatic-hydrothermal system of El Chichòn is probably related to interaction processes between a deep magmatic source and a surficial cold aquifer; an important role may also be played by the interaction of the deep fluids with the volcanic rocks and the sedimentary (limestone and evaporites) basement. The chemical and physical changes recorded in 1998–2000 were possibly due to variations in the permeability of the conduit system feeding the fluid discharges at surface, as testified by the migration of gas and water emanations. Two different scenarios can be put forward for the volcanic evolution of El Chichòn: (1) build-up of an infra-crater dome that may imply a future eruption in terms of tens to hundreds of years; (2) minor phreatic–phreatomagmatic events whose prediction and timing is more difficult to constrain. This suggests that, unlike the diminished volcanic activity at El Chichòn after the 1982 paroxistic event, the volcano-hydrothermal fluid discharges need to be more constantly monitored with regular and more frequent geochemical sampling and, at the same time, a permanent network of seismic stations should be installed.     

Multi-instrument remote and in situ observations of the Erebus Volcano (Antarctica) lava lake in 2005: A comparison with the Pele lava lake on the jovian moon Io

The stable, persistent, active lava lake at Erebus volcano (Ross Island, Antarctica) provides an excellent thermal target for analysis of spacecraft observations, and for testing new technology. In the austral summer of 2005 visible and infrared observations of the Erebus lava lake were obtained with sensors on three space vehicles Terra (ASTER, MODIS), Aqua (MODIS) and EO-1 (Hyperion, ALI). Contemporaneous ground-based observations were obtained with hand-held infrared cameras. This allowed a quantitative comparison of the thermal data obtained from different instruments, and of the analytical techniques used to analyze the data, both with and without the constraints imposed by ground-truth. From the thermal camera data, in December 2005 the main Erebus lava lake (Ray Lake) had an area of ≈ 820 m². Surface colour temperatures ranged from 575 K to 1090 K, with a broad peak in the distribution from 730 K to 850 K. Total heat loss was estimated at 23.5 MW. The flux density was ≈ 29 kW m^− 2. Mass flux was estimated at 64 to 93 kg s^− 1. The best correlation between thermal emission and emitting area was obtained with ASTER, which has the best combination of spatial resolution and wavelength coverage, especially in the thermal infrared. The high surface temperature of the lava lake means that Hyperion data are for the most part saturated. Uncertainties, introduced by the need to remove incident sunlight cause the thermal emission from the Hyperion data to be a factor of about two greater than that measured by hand-held thermal camera. MODIS also over-estimated thermal output from the lava lake by the same factor of two because it was detecting reflected sunlight from the rest of the pixel area. The measurement of the detailed temperature distribution on the surface of an active terrestrial lava lake will allow testing of thermal emission models used to interpret remote-sensing data of volcanism on Io, where no such ground-truth exists. Although the Erebus lava lake is four orders of magnitude smaller than the lava lake at Pele on Io, the shape of the integrated thermal emission spectra are similar. Thermal emission from this style of effusive volcanism appears to be invariant. Excess thermal emission in most Pele spectra (compared to Erebus) at short wavelengths (< 3 μm) is most likely due to disruption of the surface on the lava lake by escaping volatiles.     

The crater lake and hydrothermal system of Mount Pinatubo,Philippines: evolution in the decade after eruption

The June 1991 eruption of Mount Pinatubo, Philippines breached a significant, pre-eruptive magmatic-hydrothermal system consisting of a hot (>300 °C) core at two-phase conditions and surrounding, cooler (<260 °C) liquid outflows to the N and S. The eruption created a large, closed crater that accumulated hydrothermal upwellings, near-surface aquifer and meteoric inflows. A shallow lake formed by early September 1991, and showed a long-term increase in level of ~1 m/month until an artificial drainage was created in September 2001. Comparison of the temporal trends in lake chemistry to pre- and post-eruptive springs distinguishes processes important in lake evolution. The lake was initially near-neutral pH and dominated by meteoric influx and Cl–SO₄ and Cl–HCO₃ hydrothermal waters, with peaks in SO₄ and Ca concentrations resulting from leaching of anhydrite and aerosol-laden tephra. Magmatic discharge, acidity (pH~2) and rock dissolution peaked in late 1992, during and immediately after eruption of a lava dome on the crater floor. Since cessation of dome growth, trends in lake pH (increase from 3 to 5.5), temperature (decline from 40 to 26 °C), and chemical and isotopic composition indicate that magmatic degassing and rock dissolution have declined significantly relative to the input of meteoric water and immature hydrothermal brine. Higher concentrations of Cl, Na, K, Li and B, and lower concentrations of Mg, Ca, Fe, SO₄ and F up to 1999 highlight the importance of a dilute hydrothermal contribution, as do stable-isotope and tritium compositions of the various fluids. However, samples taken since that time indicate further dilution and steeper trends of increasing pH and declining temperature. Present gas and brine compositions from crater fumaroles and hot springs indicate boiling of an immature Cl–SO₄ geothermal fluid of near-neutral pH at approximately 200 °C, rather than direct discharge from magma. It appears that remnants of the pre-eruptive hydrothermal system invaded the magma conduit shortly after the end of dome emplacement, blocking the direct degassing path. This, along with the large catchment area (~5 km²) and the high precipitation rate of the area, led to a rapid transition from a small and hot acid lake to a large lake with near-ambient temperature and pH. This behavior contrasts with that of peak-activity lakes that have more sustained volcanic gas influx (e.g., Kawah Ijen, Indonesia; Poas and Rincón de la Vieja, Costa Rica).Editorial responsibility: H. Shinohara     

New geological insights and structural control on fluid circulation in La Fossa cone (Vulcano,Aeolian Islands,Italy)

Electric resistivity tomography (ERT), self-potential (SP), soil CO₂ flux, and temperature are used to study the inner structure of La Fossa cone (Vulcano, Aeolian Islands). Nine profiles were performed across the cone with a measurement spacing of 20 m. The crater rims of La Fossa cone are underlined by sharp horizontal resistivity contrasts. SP, CO₂ flux, and temperature anomalies underline these boundaries which we interpret as structural limits associated to preferential circulation of fluids. The Pietre Cotte crater and Gran Cratere crater enclose the main hydrothermal system, identified at the centre of the edifice on the base of low electrical resistivity values (<20 Ω m) and strong CO₂ degassing, SP, and temperature anomalies. In the periphery, the hydrothermal activity is also visible along structural boundaries such as the Punte Nere, Forgia Vecchia, and Palizzi crater rims and at the base of the cone, on the southern side of the edifice, along a fault attributed to the NW main tectonic trend of the island. Inside the Punte Nere crater, the ERT sections show an electrical resistive body that we interpret as an intrusion or a dome. This magmatic body is reconstructed in 3D using the available ERT profiles. Its shape and position, with respect to the Pietre Cotte crater fault, allows replacing this structure in the chronology of the development of the volcano. It corresponds to a late phase of activity of the Punte Nere edifice. Considering the position of the SP, soil CO₂ flux, and temperature maxima and the repartition of conductive zones related to hydrothermal circulation with respect to the main structural features, La Fossa cone could be considered as a relevant example of the strong influence of pre-existing structures on hydrothermal fluid circulation at the scale of a volcanic edifice.     

Subaqueous geothermal activity revealed by lacustrine sediments of the acidic Nakadake crater lake, Aso Volcano, Japan

Lacustrine sediments were sampled from the inaccessible acidic (pH = 0.43) Nakadake crater lake of Aso Volcano, Japan by a simple method. The sediments contain an extremely high content (74 wt.%) of sulfur, which exits as elemental sulfur, gypsum and anhydrite. The abundant elemental sulfur is likely formed by the reaction of SO₂ and H₂S gases and by the SO₂ disproportionation reaction in magmatic hydrothermal system below the crater lake. Based on the sulfur content of sediments and measurements of elevation change of the crater bottom, the sulfur accumulation rate at the Nakadake crater lake was calculated as 250 tonne/day, which is comparable with the SO₂ emission rate (200–600 tonne/day) from the Nakadake crater. The sediments include a small amount (9%) of clear glass shards that are apparently not altered in spite of the high reactivity of hyperacid lake water. This finding suggests that the clear glass shards are fragments of recently emitted magmas from fumaroles on the bottom of the crater lake and the magma emissions continuously occur even in quiescent periods.     

The Upper Valanginian (Early Cretaceous) positive carbon-isotope event recorded in terrestrial plants

Our understanding of the ancient ocean-atmosphere system has focused on oceanic proxies. However, the study of terrestrial proxies is equally necessary to constrain our understanding of ancient climates and linkages between the terrestrial and oceanic carbon reservoirs. We have analyzed carbon-isotope ratios from fossil plant material through the Valanginian and Lower Hauterivian from a shallow-marine, ammonite-constrained succession in the Crimean Peninsula of the southern Ukraine in order to determine if the Upper Valanginian positive carbon-isotope excursion is expressed in the atmosphere. δ¹³C_plant values fluctuate around − 23‰ to − 22‰ for the Valanginian-Hauterivian, except during the Upper Valanginian where δ¹³C_plant values record a positive excursion to ∼− 18‰. Based upon ammonite biostratigraphy from Crimea, and in conjunction with a composite Tethyan marine δ¹³C_carb curve, several conclusions can be drawn: (1) the δ¹³C_plant record indicates that the atmospheric carbon reservoir was affected; (2) the defined ammonite correlations between Europe and Crimea are synchronous; and (3) a change in photosynthetic carbon-isotope fractionation, caused by a decrease in atmospheric pCO₂, occurred during the Upper Valanginian positive δ¹³C excursion. Our new data, combined with other paleoenvironmental and paleoclimatic information, indicate that the Upper Valanginian was a cool period (icehouse) and highlights that the Cretaceous period was interrupted by periods of cooling and was not an equable climate as previously thought.     

Stable and radiogenic isotopes as tracers for the origin,mixing and subsurface history of fluids in submarine shallow-water hydrothermal systems

The shallow-water hydrothermal system in Tutum Bay on the west side of Ambitle Island, Papua New Guinea provides us with an exceptional opportunity to study isotope systematics in a near shore setting. Compared to seawater, the hydrothermal fluids in Tutum Bay have lower values for δD, δ¹⁸O, δ¹³C, and ⁸⁷Sr and higher values for ³H, δ³⁴S(SO₄) and δ¹⁸O(SO₄). The δ¹⁸O and δD records for vents 1 and 4 indicate that fluid compositions remained stable over an extended period. Interpretation of isotope data clearly demonstrates the predominantly meteoric origin of Tutum Bay hydrothermal fluids, despite their location in a marine environment. δ¹⁸O and δD values are identical to mean average annual precipitation in eastern Papua New Guinea. The hypothesis that these fluids are a simple product of mixing between seawater and onshore hydrothermal fluids from the Waramung (W-1) and Kapkai (W-2) thermal areas has been rejected, because the observed δ³⁷Cl, ³H, δ³⁴S(SO₄) and δ¹⁸O(SO₄) values cannot be explained by a simple mixing model. The application of δ¹⁸O(SO₄) and δ¹³C thermometers in combination with ³H values corroborates the three-step model of Pichler et al. [Pichler, T., Veizer, J., Hall, G.E.M., 1999. The chemical composition of shallow-water hydrothermal fluids in Tutum Bay, Ambitle Island, Papua New Guinea and their effect on ambient seawater. Marine Chemistry 64 (3) 229–252], where (1) phase separation in the deep reservoir beneath Ambitle Island produces a high temperature vapor that rises upward and subsequently reacts with cooler ground water to form a low pH, CO₂-rich water of approximately 150–160 °C, (2) caused by the steep topography, this CO₂-rich fluid moves laterally towards the margin of the hydrothermal system where it mixes with the marginal upflow of the deep reservoir fluid. This produces a dilute chloride water of approximately 165 °C, and (3) possibly the entrainment of minor amounts of ground or seawater during its final ascent.     

Geochemistry of the Albano and Nemi crater lakes in the volcanic district of Alban Hills (Rome,Italy)

Lake Albano, located 20 km to the SE of Rome, is hosted within the most recent crater of the quiescent Alban Hills volcanic complex that produced hydromagmatic eruptions in Holocene times. Stratigraphic, archaeological and historical evidence indicates that the lake level underwent important variations in the Bronze Age. Before the IV century B.C. several lahars were generated by water overflows from the lake and in the IV century B.C. Romans excavated a drainage tunnel. The lake is located above a buried carbonate horst that contains a pressurized medium-enthalpy geothermal reservoir from which fluids escape to the surface to produce many important gas manifestations of mostly CO₂. Previous studies recognized the presence of gas emissions also from the crater bottom. In 1997 the possibility of a Nyos-type event triggered by a lake rollover was considered very low, because the CO₂ water concentration at depth was found to be far from saturation. However, considering the high population density nearby, the Italian Civil Protection Department recommended that periodical monitoring be carried out. To this scope we initiated in 2001 a systematic geochemical study of the lake. Thirteen vertical profiles have been repeatedly carried out in 2001–2006, especially in the deepest part of the lake (167 m in 2006), measuring T, pH, dissolved O₂ and electrical conductivity. Water samples were collected from various depths and chemically and isotopically analysed. Two similar profiles have been measured also in the nearby Nemi crater lake. Results indicate that in the 4.5 years of monitoring the pressure of gas dissolved in the Lake Albano deep waters remained much lower than the hydrostatic pressure. A CO₂ soil survey carried out on the borders of the two lakes, indicates the presence of some zones of anomalous degassing of likely magmatic origin. A water overturn or a heavy mixing of deep and shallow waters likely occurred in winter 2003–2004, when cold rainfall cooled the surface water below 8.5 °C. Such overturns cause only a limited gas exsolution from the lake when the deep water is brought to a few meters depth but can explain the observed decrease with time of dissolved CO₂ at depth and related water pH increase. A gas hazard could occur in the case of a sudden injection through the lake bottom of a huge quantity of CO₂-rich fluids, which might be caused by earthquake induced fracturing of the rock pile beneath the lake. A limnic gas eruption might also occur should CO₂ concentration build up within the lake for a long time.     

Evolution of the oceanic calcium cycle during the late Mesozoic: Evidence from δ44/40Ca of marine skeletal carbonates

The Ca isotope compositions of 37 late Mesozoic skeletal carbonates, belemnites and brachiopods, from the Tethyan realm were analyzed by thermal (TIMS) and plasma (MC-ICP-MS) ionization mass spectrometry. A poor correlation between δ^44/40Ca and δ¹⁸O values of belemnites suggests only a weak temperature dependency for the Ca isotope composition of belemnites, likely less than 0.02‰/°C. The δ^44/40Ca record of belemnites was therefore used to reconstruct the Ca isotope composition of paleo-seawater (δ^44/40Ca_SW), based on an experimentally determined fractionation factor between seawater Ca and belemnite calcite (α_CC–SW) of ∼ 0.9986. The inferred δ^44/40Ca_SW record, with an average stratigraphic resolution of 1 Ma, shows systematic temporal variation of ∼ 0.5‰ with the Middle/Late Jurassic (∼ 154 Ma) minimum of ∼ 1.4‰ and a subsequent general increase to the Early Cretaceous (∼ 124 Ma) maximum of ∼ 1.9‰. The global nature of the δ^44/40Ca_SW record is supported by identical Ca isotope compositions of coeval (Kimmeridgian) belemnites collected from two distinct paleogeographic regions, the southern (New Zealand) and northern (Germany) margin of the Tethys Ocean. The observed late Mesozoic δ^44/40Ca_SW record was simulated using a simple Ca isotope mass balance model, and the results indicate that the variation in δ^44/40Ca_SW record can be explained by changes in oceanic input fluxes of Ca that were independent of the carbonate ion fluxes, such as the hydrothermal Ca flux or the release of Ca to the oceans via dolomitization of marine carbonates.     

Degassing patterns of Tungurahua volcano (Ecuador) during the 1999–2006 eruptive period,inferred from remote spectroscopic measurements of SO2 emissions

This paper presents the results of 7 years (Aug. 1999–Oct. 2006) of SO₂ gas measurements during the ongoing eruption of Tungurahua volcano, Ecuador. From 2004 onwards, the operation of scanning spectrometers has furnished high temporal resolution measurements of SO₂ flux, enabling this dataset to be correlated with other datasets, including seismicity. The emission rate of SO₂ during this period ranges from less than 100 to 35,000 tonnes/day (t d^− 1) with a mean daily emission rate of 1458 t d^− 1 and a standard deviation of ± 2026 t d^− 1. Average daily emissions during inferred explosive phases are about 1.75 times greater than during passive degassing intervals. The total amount of sulfur emitted since 1999 is estimated as at least 1.91 Mt, mostly injected into the troposphere and carried westwards from the volcano. Our observations suggest that the rate of passive degassing at Tungurahua requires SO₂ exsolution of an andesitic magma volume that is two orders of magnitude larger than expected for the amount of erupted magma. Two possible, and not mutually exclusive, mechanisms are considered here to explain this excess degassing: gas flow through a permeable stagnant-magma-filled conduit and gas escape from convective magma overturning in the conduit. We have found that real-time gas monitoring contributes significantly to better eruption forecasting at Tungurahua, because it has provided improved understanding of underlying physical mechanisms of magma ascent and eruption.     

Effects of an estuarine plume-associated bloom on the carbonate system in the lower reaches of the Pearl River estuary and the coastal zone of the northern South China Sea

We observed a phytoplankton bloom downstream of a large estuarine plume induced by heavy precipitation during a cruise conducted in the Pearl River estuary and the northern South China Sea in May–June 2001. The plume delivered a significant amount of nutrients into the estuary and the adjacent coastal region, and enhanced stratification stimulating a phytoplankton bloom in the region near and offshore of Hong Kong. A several fold increase (0.2–1.8 μg Chl L⁻¹) in biomass (Chl a) was observed during the bloom. During the bloom event, the surface water phytoplankton community structure significantly shifted from a pico-phytoplankton dominated community to one dominated by micro-phytoplankton (>20 μm). In addition to increased Chl a, we observed a significant drawdown of pCO₂, biological uptake of dissolved inorganic carbon (DIC) and an associated enhancement of dissolved oxygen and pH, demonstrating enhanced photosynthesis during the bloom. During the bloom, we estimated a net DIC drawdown of 100–150 μmol kg⁻¹ and a TAlk increase of 0–50 μmol kg⁻¹. The mean sea–air CO₂ flux at the peak of the bloom was estimated to be as high as ∼−18 mmol m⁻² d⁻¹. For an average surface water depth of 5 m, a very high apparent biological CO₂ consumption rate of 70–110 mmol m⁻² d⁻¹ was estimated. This value is 2–6 times higher than the estimated air–sea exchange rate.     

Low-temperature hydrothermal alteration of intra-caldera tuffs,Miocene Tejeda caldera,Gran Canaria,Canary Islands

The Miocene Tejeda caldera on Gran Canaria erupted ~ 20 rhyolite–trachyte ignimbrites (Mogán Group 14–13.3 Ma), followed by ~ 20 phonolitic lava flows and ignimbrites (Fataga Group 13–8.5 Ma). Upper-Mogán tuffs have been severely altered immediately within the caldera margin, whereas extra-caldera Mogán ignimbrites, and overlying Fataga units, are apparently unaltered. The altered intra-caldera samples contain minerals characteristic of secondary fluid–rock interaction (clays, zeolites, adularia), and relics of the primary mineral assemblage identified in unaltered ignimbrites (K-feldspar, plagioclase, pyroxene, amphibole, and groundmass quartz). Major and trace-element data indicate that Si, Na, K, Pb, Sr, and Rb, were strongly mobilized during fluid–rock interaction, whereas Ti, Zr, and Nb behaved in a more refractory manner, experiencing only minor mobilization. The δ¹⁸O values of the altered intra-caldera tuffs are significantly higher than in unaltered extra-caldera ignimbrites, consistent with an overall low-temperature alteration environment. Unaltered extra-caldera ignimbrites have δD values between − 110‰ and − 173‰, which may reflect Rayleigh-type magma degassing and/or post-depositional vapour release. The δD values of the altered intra-caldera tuffs range from − 52‰ to − 131‰, with ambient meteoric water at the alteration site estimated at ca. − 15‰. Interaction and equilibration of the intra-caldera tuffs with ambient meteoric water at low temperature can only account for whole-rock δD values of around − 45‰, given that ?D_clay–water is ca. − 30‰ at 100 °C, and decreases in magnitude at higher temperatures. All altered tuff samples have δD values that are substantially lower than − 45‰, indicating interaction with a meteoric water source with a δD value more negative than − 15‰, which may have been produced in low-temperature steam fumaroles. Supported by numerical modeling, our Gran Canaria data reflect the near-surface, epithermal part of a larger, fault-controlled hydrothermal system associated with the emplacement of the high-level Fataga magma chamber system. In this near-surface environment, fluid temperatures probably did not exceed 200–250 °C.     

Air-sea CO2 fluxes in the southern Yellow Sea: An examination of the continental shelf pump hypothesis

The southern Yellow Sea (SYS), located to the north of the East China Sea (ECS), was considered part of the ECS when Tsunogai et al. (1999) proposed the “continental shelf pump” (CSP) hypothesis. However, the original CSP carbon dioxide (CO₂) uptake flux (2.9 mol C m⁻² yr⁻¹) appears to have been overestimated, primarily due to the differences between the SYS and the ECS in terms of their CO₂ system. In this paper, we estimated air-sea CO₂ fluxes in the SYS using the surface water partial pressure of CO₂ (pCO₂) measured in winter, spring, and summer, as well as that estimated in fall via the relationship of pCO₂ with salinity, temperature, and chlorophyll a. The results indicate that overall, the entire investigated area was a net source of atmospheric CO₂ during summer, winter, and fall, whereas it was a net sink during spring. Spatially, the nearshore area was almost a permanent CO₂ source, while the central SYS shifted from being a CO₂ sink in spring to a source in the other seasons of the year. Overall, the SYS is a net source of atmospheric CO₂ on an annual scale, releasing ∼7.38 Tg C (1 Tg=10¹² g) to the atmosphere annually. Thus, the updated CO₂ uptake flux in the combined SYS and ECS is reduced to ∼0.86 mol C m⁻² yr⁻¹. If this value is extrapolated globally following Tsunogai et al. (1999), the global continental shelf would be a sink of ∼0.29 Pg C yr⁻¹, instead of 1 Pg C yr⁻¹ (1 Pg=10¹⁵ g).The SYS as a net annual source of atmospheric CO₂ is in sharp contrast to most mid- and high-latitude continental shelves, which are CO₂ sinks. We argue that unlike the ECS and the North Sea where carbon on the shelf could be exported to the open ocean, the SYS lacks the physical conditions required by the CSP to transport carbon off the shelf effectively. The global validity of the CSP theory is thus questionable.