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.     

Eddy covariance imaging of diffuse volcanic CO<Subscript>2</Subscript> emissions at Mammoth Mountain,CA, USA

Use of eddy covariance (EC) techniques to map the spatial distribution of diffuse volcanic CO₂ fluxes and quantify CO₂ emission rate was tested at the Horseshoe Lake tree-kill area on Mammoth Mountain, California, USA. EC measurements of CO₂ flux were made during September–October 2010 and ranged from 85 to 1,766 g m⁻² day⁻¹. Comparative maps of soil CO₂ flux were simulated and CO₂ emission rates estimated from three accumulation chamber (AC) CO₂ flux surveys. Least-squares inversion of measured eddy covariance CO₂ fluxes and corresponding modeled source weight functions recovered 58–77% of the CO₂ emission rates estimated based on simulated AC soil CO₂ fluxes. Spatial distributions of modeled surface CO₂ fluxes based on EC and AC observations showed moderate to good correspondence (R ² = 0.36 to 0.70). Results provide a framework for automated monitoring of volcanic CO₂ emissions over relatively large areas.     

Limestone assimilation and the origin of CO2 emissions at the Alban Hills (Central Italy): Constraints from experimental petrology

The Alban Hills volcanic region (20 km south of Rome, in the Roman Province) emitted a large volume of potassic magmas (> 280 km³) during the Quaternary. Chemical interactions between ascending magmas and the ∼ 7000–8000-m-thick sedimentary carbonate basement are documented by abundant high temperature skarn xenoliths in the eruptive products and have been frequently corroborated by geochemical surveys. In this paper we characterize the effect of carbonate assimilation on phase relationships at 200 MPa and 1150–1050 °C by experimental petrology. Calcite and dolomite addition promotes the crystallization of Ca-rich pyroxene and Mg-rich olivine respectively, and addition of both carbonates results in the desilication of the melt. Furthermore, carbonate assimilation liberates a large quantity of CO₂-rich fluid. A comparison of experimental versus natural mineral, glass and bulk rock compositions suggests large variations in the degree of carbonate assimilation for the different Alban Hills eruptions. A maximum of 15 wt.% assimilation is suggested by some melt inclusion and clinopyroxene compositions; however, most of the natural data indicate assimilation of between 3 and 12 wt.% carbonate. Current high CO₂ emissions in this area most likely indicate that such an assimilation process still occurs at depth. We calculate that a magma intruding into the carbonate basement with a rate of ∼ 1 – 2 · 10⁶ m³/year, estimated by geophysical studies, and assimilating 3–12 wt.% of host rocks would release an amount of CO₂ matching the current yearly emissions at the Alban Hills. Our results strongly suggest that current CO₂ emissions in this region are the shallow manifestation of hot mafic magma intrusion in the carbonate-hosted reservoir at 5–6 km depth, with important consequences for the present-day volcanic hazard evaluation in this densely populated and historical area.     

First <Superscript>13</Superscript>C/<Superscript>12</Superscript>C isotopic characterisation of volcanic plume CO<Subscript>2</Subscript>

We describe analytical details and uncertainty evaluation of a simple technique for the measurement of the carbon isotopic composition of CO₂ in volcanic plumes. Data collected at Solfatara and Vulcano, where plumes are fed by fumaroles which are accessible for direct sampling, were first used to validate the technique. For both volcanoes, the plume-derived carbon isotopic compositions are in good agreement with the fumarolic compositions, thus providing confidence on the method, and allowing its application at volcanoes where the volcanic component is inaccessible to direct sampling. As a notable example, we applied the same method to Mount Etna where we derived a δ¹³C of volcanic CO₂ between −0.9 ± 0.27‰ and −1.41 ± 0.27‰ (Bocca Nuova and Voragine craters). The comparison of our measurements to data reported in previous work highlights a temporal trend of systematic increase of δ¹³C values of Etna CO₂ from ~ −4‰, in the 1970’s and the 1980’s, to ~ −1‰ at the present time (2009). This shift toward more positive δ¹³C values matches a concurrent change in magma composition and an increase in the eruption frequency and energy. We discuss such variations in terms of two possible processes: magma carbonate assimilation and carbon isotopic fractionation due to magma degassing along the Etna plumbing system. Finally, our results highlight potential of systematic measurements of the carbon isotopic composition of the CO₂ emitted by volcanic plumes for a better understanding of volcanic processes and for improved surveillance of volcanic activity.     

Biogeochemical processes involving dissolved CO2 and CH4 at Albano, Averno, and Monticchio meromictic volcanic lakes (Central–Southern Italy)

This paper focuses on the chemical and isotopic features of dissolved gases (CH₄ and CO₂) from four meromictic lakes hosted in volcanic systems of Central–Southern Italy: Lake Albano (Alban Hills), Lake Averno (Phlegrean Fields), and Monticchio Grande and Piccolo lakes (Mt. Vulture). Deep waters in these lakes are characterized by the presence of a significant reservoir of extra-atmospheric dissolved gases mainly consisting of CH₄ and CO₂. The δ¹³C-CH₄ and δD-CH₄ values of dissolved gas samples from the maximum depths of the investigated lakes (from ?66.8 to ?55.6?‰ V-PDB and from ?279 to ?195?‰ V-SMOW, respectively) suggest that CH₄ is mainly produced by microbial activity. The δ¹³C-CO₂ values of Lake Grande, Lake Piccolo, and Lake Albano (ranging from ?5.8 to ?0.4?‰ V-PDB) indicate a significant CO₂ contribution from sublacustrine vents originating from (1) mantle degassing and (2) thermometamorphic reactions involving limestone, i.e., the same CO₂ source feeding the regional thermal and cold CO₂-rich fluid emissions. In contrast, the relatively low δ¹³C-CO₂ values (from ?13.4 to ?8.2?‰ V-PDB) of Lake Averno indicate a prevalent organic CO₂. Chemical and isotopic compositions of dissolved CO₂ and CH₄ at different depths are mainly depending on (1) CO₂ inputs from external sources (hydrothermal and/or anthropogenic); (2) CO₂–CH₄ isotopic exchange; and (3) methanogenic and methanotrophic activity. In the epilimnion, vertical water mixing, free oxygen availability, and photosynthesis cause the dramatic decrease of both CO₂ and CH₄ concentrations. In the hypolimnion, where the δ¹³C-CO₂ values progressively increase with depth and the δ¹³C-CH₄ values show an opposite trend, biogenic CO₂ production from CH₄ using different electron donor species, such as sulfate, tend to counteract the methanogenesis process whose efficiency achieves its climax at the water–bottom sediment interface. Theoretical values, calculated on the basis of δ¹³C-CO₂ values, and measured δ¹³C_TDIC values are not consistent, indicating that CO₂ and the main carbon-bearing ion species (HCO₃ ^?) are not in isotopic equilibrium, likely due to the fast kinetics of biochemical processes involving both CO₂ and CH₄. This study demonstrates that the vertical patterns of the CO₂/CH₄ ratio and of δ¹³C-CO₂ and δ¹³C-CH₄ are to be regarded as promising tools to detect perturbations, related to different causes, such as changes in the CO₂ input from sublacustrine springs, that may affect aerobic and anaerobic layers of meromictic volcanic lakes.     

Eruptive history and petrologic evolution of the Albano multiple maar (Alban Hills, Central Italy)

A comprehensive volcanological study of the Albano multiple maar (Alban Hills, Italy) using (i) ⁴⁰Ar/³⁹Ar geochronology of the most complete stratigraphic section and other proximal and distal outcrops and (ii) petrographic observations, phase analyses of major and trace elements, and Sr and O isotopic analyses of the pyroclastic deposits shows that volcanic activity at Albano was strongly discontinuous, with a first eruptive cycle at 69±1 ka producing at least two eruptions, and a second cycle with two peaks at 39±1 and 36±1 ka producing at least four eruptions. Contrary to previous studies, we did not find evidence of magmatic or hydromagmatic eruptions younger than 36±1 ka. The activity of Albano was fed by a new batch of primary magma compositionally different from that of the older activity of the Alban Hills; moreover, the REE and ⁸⁷Sr/⁸⁶Sr data indicate that the Albano magma originated from an enriched metasomatized mantle. According to the modeled liquid line of descent, this magma differentiated under the influence of magma/limestone wall rock interaction. Our detailed eruptive and petrologic reconstruction of the Albano Maar evolution substantiates the dormant state of the Alban Hills Volcanic District. Electronic Supplementary Material Supplementary material is available for this article at Editorial responsibility: J. Donnelly-Nolan An erratum to this article can be found at     

CO<Subscript>2</Subscript> and He degassing at El Chichón volcano,Chiapas, Mexico: gas flux,origin and relationship with local and regional tectonics

During 2007–2008, three CO₂ flux surveys were performed on El Chichón volcanic lake, Chiapas, Mexico, with an additional survey in April 2008 covering the entire crater floor (including the lake). The mean CO₂ flux calculated by sequential Gaussian simulation from the lake was 1,190 (March 2007), 730 (December 2007) and 1,134 g m⁻² day⁻¹ (April 2008) with total emission rates of 164 ± 9.5 (March 2007), 59 ± 2.5 (December 2007) and 109 ± 6.6 t day⁻¹ (April 2008). The mean CO₂ flux estimated from the entire crater floor area was 1,102 g m⁻² day⁻¹ for April 2008 with a total emission rate of 144 ± 5.9 t day⁻¹. Significant change in CO₂ flux was not detected during the period of survey, and the mapping of the CO₂ flux highlighted lineaments reflecting the main local and regional tectonic patterns. The ³He/⁴He ratio (as high as 8.1 R _A) for gases in the El Chichón crater is generally higher than those observed at the neighbouring Transmexican Volcanic Belt and the Central American Volcanic Arc. The CO₂/³He ratios for the high ³He/⁴He gases tend to have the MORB-like values (1.41 × 10⁹), and the CO₂/³He ratios for the lower ³He/⁴He gases fall within the range for the arc-type gases. The high ³He/⁴He ratios, the MORB-like CO₂/³He ratios for the high ³He/⁴He gases and high proportion of MORB-CO₂ (M = 25 ±15%) at El Chichón indicate a greater depth for the generation of magma when compared to typical arc volcanoes.     

Low carbon dioxide partial pressure in a productive subtropical lake

The purposes of this study were to assess if Lake Apopka (FL, USA) was autotrophic or heterotrophic based on the partial pressure of dissolved carbon dioxide (pCO₂) in the surface water and to evaluate factors that influence the long-term changes in pCO₂. Monthly average pH, alkalinity and other limnological variables collected between 1987 and 2006 were used to estimate dissolved inorganic carbon (DIC), pCO₂ and CO₂ flux between surface water and atmosphere. Results indicated that average pCO₂ in the surface water was 196 μatm, well below the atmospheric pCO₂. Direct measurements of DIC concentration on three sampling dates in 2009 also supported pCO₂ undersaturation in Lake Apopka. Supersaturation in CO₂ occurred in this lake in only 13% of the samples from the 20-year record. The surface-water pCO₂ was inversely related to Chl a concentrations. Average annual CO₂ flux was 28.2 g C m⁻² year⁻¹ from the atmosphere to the lake water and correlated significantly with Chl a concentration, indicating that biological carbon sequestration led to the low dissolved CO₂ concentration. Low pCO₂ and high invasion rates of atmospheric CO₂ in Lake Apopka indicated persistent autotrophy. High rates of nutrient loading and primary production, a high buffering capacity, a lack of allochthonous loading of organic matter, and the dominance of a planktivorous–benthivorous fish food web have supported long-term net autotrophy in this shallow subtropical eutrophic lake. Our results also showed that lake restoration by the means of nutrient reduction resulted in significantly lower total phosphorus (TP) and Chl a concentrations, and higher pCO₂.     

Simulating CO<Subscript>2</Subscript> transport into the ocean from a CO<Subscript>2</Subscript> lake at the seafloor using a <Emphasis Type="Italic">z</Emphasis>- and a <Emphasis Type="Italic">σ</Emphasis>-coordinate model

The ocean takes up approximately 2 GT carbon per year due to the enhanced CO₂ concentrations in the atmosphere. Several options have been suggested in order to reduce the emissions of CO₂ into the atmosphere, and among these are CO₂ storage in the deep ocean. Topographic effects of dissolution and transport from a CO₂ lake located at 3,000-m depth have been studied using the z-coordinate model Massachusetts Institute of Technology general circulation model (MITgcm) and the σ-coordinate model Bergen ocean model (BOM). Both models have been coupled with the general ocean turbulence model (GOTM) in order to account for vertical subgrid processes. The chosen vertical turbulence mixing scheme includes the damping effect from stable stratification on the turbulence intensity. Three different topographic scenarios are presented: a flat bottom and the CO₂ lake placed within a trench with depths of 10 and 20 m. The flat case scenario gives good correlation with previous numerical studies of dissolution from a CO₂ lake. When topography is introduced, it is shown that the z-coordinate model and the σ-coordinate model give different circulation patterns in the trench. This leads to different dissolution rates, 0.1 μmol cm^− 2 s^− 1 for the scenario of a 20-m-deep trench using BOM and 0.005–0.02 μmol cm^− 2 s^− 1 for the same scenario using the MITgcm. The study is also relevant for leakages of CO₂ stored in geological formations and to the ocean.     

Crustal structure, evolution, and volcanic unrest of the Alban Hills, Central Italy

 The Alban Hills, a Quaternary volcanic center lying west of the central Apennines, 15–25 km southeast of Rome, last erupted 19 ka and has produced approximately 290 km³ of eruptive deposits since the inception of volcanism at 580 ka. Earthquakes of moderate intensity have been generated there at least since the Roman age. Modern observations show that intermittent periods of swarm activity originate primarily beneath the youngest features, the phreatomagmatic craters on the west side of the volcano. Results from seismic tomography allow identification of a low-velocity region, perhaps still hot or partially molten, more than 6 km beneath the youngest craters and a high-velocity region, probably a solidified magma body, beneath the older central volcanic construct. Thirty centimeters of uplift measured by releveling supports the contention that high levels of seismicity during the 1980s and 1990s resulted from accumulation of magma beneath these craters. The volume of magma accumulation and the amount of maximum uplift was probably at least 40×10⁶ m³ and 40 cm, respectively. Comparison of newer levelings with those completed in 1891 and 1927 suggests earlier episodes of uplift. The magma chamber beneath the western Alban Hills is probably responsible for much of the past 200 ka of eruptive activity, is still receiving intermittent batches of magma, and is, therefore, continuing to generate modest levels of volcanic unrest. Bending of overburden is the most likely cause of the persistent earthquakes, which generally have hypocenters above the 6-km-deep top of the magma reservoir. In this view, the most recent uplift and seismicity are probably characteristic and not precursors of more intense activity. Received: 15 April 1997 / Accepted: 9 August 1997     

Post-caldera activity in the Alban Hills volcanic district (Italy): 40Ar/39Ar geochronology and insights into magma evolution

We present 24 ⁴⁰Ar/³⁹Ar ages for the youngest volcanic products from the Alban Hills volcanic district (Rome). Combined with petrological data on these products, we have attempted to define the chronology of the most recent phase of activity and to investigate the magma evolution of this volcanic district. The early, mainly explosive activity of the Alban Hills spanned the interval from 561±1 to 351±3 ka. After approximately 50-kyr of dormancy, a mainly effusive phase of activity took place, accompanied by the strombolian activity of a small central edifice (Monte delle Faete). This second phase of activity spanned the interval 308±2 to 250±1 ka. After another dormancy period of approximately 50-kyr, a new, hydromagmatic phase of activity started at 200 ka at several centers located to the southwest of the Monte delle Faete edifice. After an initial recurrence period of approximately 50-kyr, which also characterized this new phase of activity, the longest dormancy period (approximately 80-kyr) in the history of the volcanic district preceded the start of the activity of the Albano and Giuturna centers at 70±1 ka. Results of our study suggest a quasi-continuous magmatic activity feeding hydromagmatic centers with a new acme of volcanism since around 70 ka. Based on data presented in this paper, we argue that the Alban Hills should not be considered an extinct volcanic district and a detailed re-assessment of the volcanic hazard for the area of Rome is in order. Published online: 4 April 2003 Editorial responsibility: J. Donnelly-Nolan     

The Albano maar lake (Colli Albani Volcano, Italy): recent volcanic activity and evidence of pre-Roman Age catastrophic lahar events

The evaluation of volcanic hazard in the Roman hinterland related to the quiescent Colli Albani Volcano has recently been the subject of renewed attention and several interpretations by many authors. However, very little was known of the recent history of the volcano, making such interpretations rather speculative. The most recent activity of Colli Albani Volcano originated from the Albano polygenetic maar lake, which erupted several phreatomagmatic units, the most recent of which, the Peperino Albano ignimbrite, has been dated at around 25 ka. An area of several square kilometers centered around Albano Lake is presently the site of shallow and frequent seismic activity and gaseous emission as well as hydrothermal activity and is therefore considered the most prone to geologic hazards. This paper presents new stratigraphic and geomorphologic data as well as age determinations that allow rejuvenation of the most recent activity of the Colli Albani Volcano, and particularly the Albano maar lake, to the Holocene. This study allows for the first time to identify a potential hazard related to the Albano maar lake withdrawal interpreted to be related to endogenous causes, namely CO₂ emission. The main results of the study are: (1) the Peperino Albano is not, as is generally believed, the last phreatomagmatic eruption from the Colli Albani Volcano; a previously unrecognized phreatomagmatic surge deposit has been identified overlying the paleosol at the top of the Peperino Albano and related lahar deposits; (2) two lahar deposits separated by paleosols top the stratigraphic succession and are dispersed only to the NW, corresponding to the lowest point of the maar rim, indicating that catastrophic hydrologic events occurred at the Albano Lake in recent times; rapid and substantial lake-level variations and lake withdrawal are reported by Roman historians and recorded by the stratigraphy of the Albano Lake lacustrine sediments; (3) microfracturing related to seismic energy release is linked to sudden variation of CO₂ flow and upwelling of hydrothermal fluids. These occurrences across the lake are the likely causes that triggered during Holocene several episodes of lake withdrawal, rising the water table and probably triggering convective rollover of the lake water.     

Sulphur emissions to the stratosphere from explosive volcanic eruptions

 Two methods were used to quantify the flux of volcanic sulphur (as the equivalent mass of SO₂) to the stratosphere over different timescales during the Holocene. A combination of satellite-based measurements of sulphur yields from recent explosive volcanic eruptions with an appropriate rate of explosive volcanism for the past 200 years constrains the medium-term (∼10²years) flux of volcanic sulphur to the stratosphere to be ∼1 Mt a^–1, with lower and upper bounds of 0.3 and 3 Mt a^–1. The short-term (∼10- to 20-year) flux due to small magnitude (10¹⁰–10¹²kg) eruptions is of the order of 0.4 Mt a^–1. At any time the instantaneous levels of sulphur in the stratosphere are dominated by the most recent (0–3 years) volcanic events. The flux calculations do not attempt to address this very short timescale variability. Although there are significant errors associated with the raw sulphur emission data on which this analysis is based, the approach presented is general and may be readily modified as the quantity and quality of the data improve. Data from a Greenland ice core support these conclusions. Integration of the sulphate signals from presumed volcanic sources recorded in the GISP2 core provides a minimum estimate of the 10³–year volcanic SO₂ flux to the stratosphere of 0.5–1 Mt a^–1 over the past 9000 years. The short-term flux calculations do not account for the impact of rare, large events. The ice-core record does not fully account for the contribution from small, frequent events. Received: 27 September 1995 / Accepted: 13 December 1995     

Modelling the dynamics and thermodynamics of volcanic degassing

 The rates of passive degassing from volcanoes are investigated by modelling the convective overturn of dense degassed and less dense gas-rich magmas in a vertical conduit linking a shallow degassing zone with a deep magma chamber. Laboratory experiments are used to constrain our theoretical model of the overturn rate and to elaborate on the model of this process presented by Kazahaya et al. (1994). We also introduce the effects of a CO₂–saturated deep chamber and adiabatic cooling of ascending magma. We find that overturn occurs by concentric flow of the magmas along the conduit, although the details of the flow depend on the magmas' viscosity ratio. Where convective overturn limits the supply of gas-rich magma, then the gas emission rate is proportional to the flow rate of the overturning magmas (proportional to the density difference driving convection, the conduit radius to the fourth power, and inversely proportional to the degassed magma viscosity) and the mass fraction of water that is degassed. Efficient degassing enhances the density difference but increases the magma viscosity, and this dampens convection. Two degassing volcanoes were modelled. At Stromboli, assuming a 2 km deep, 30% crystalline basaltic chamber, containing 0.5 wt.% dissolved water, the ∼700 kg s^–1 magmatic water flux can be modelled with a 4–10 m radius conduit, degassing 20–100% of the available water and all of the 1 to 4 vol.% CO₂ chamber gas. At Mount St. Helens in June 1980, assuming a 7 km deep, 39% crystalline dacitic chamber, containing 4.6 wt.% dissolved water, the ∼500 kg s^–1 magmatic water flux can be modelled with a 22–60 m radius conduit, degassing ∼2–90% of the available water and all of the 0.1 to 3 vol.% CO₂ chamber gas. The range of these results is consistent with previous models and observations. Convection driven by degassing provides a plausible mechanism for transferring volatiles from deep magma chambers to the atmosphere, and it can explain the gas fluxes measured at many persistently active volcanoes. Received: 26 September 1997 / Accepted: 11 July 1998     

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

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

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     

不同水文情景下洪泽湖二氧化碳排放通量特征及影响因素

内陆水域二氧化碳(CO₂)排放是全球碳平衡的重要组成部分,全球CO₂排放通量估算通常有很大不确定性,一方面源于CO₂排放数据观测的时空离散性,另一方面也是缺少水文情景与CO₂排放通量关联性的研究.本文观测了2018年洪泽湖不同水文情景表层水体CO₂排放通量特征,并探讨其影响因素.结果表明,洪泽湖CO₂排放通量为丰水期((106.9±73.4) mmol/(m²·d))>枯水期((18.7±13.6) mmol/(m²·d))>平水期((5.2±15.5) mmol/(m²·d)),且碳通量由丰(310.2~32.0 mmol/(m²·d))、枯(50.8~2.2 mmol/(m²·d))、平(-17.3~39.8 mmol/(m²·d))3种水文情景的交替表现出湖泊碳源到弱碳汇的转变,空间上CO₂排放通量总体呈现北部成子湖区低、南部过水湖区高的分布趋势.洪泽湖CO₂排放对水文情景响应敏感,特别是上游淮河流域来水量的改变,是主导该湖CO₂排放时空分异的重要因子.丰水期湖泊接纳了淮河更多有机和无机碳的输入,外源碳基质的降解和矿化显著促进了水体CO₂的生产与排放,同时氮、磷等营养物质的大量输入,加剧了水体营养化程度,进一步提高CO₂排放量,间接反映出人类活动对洪泽湖CO₂变化的深刻影响.平、枯水期随着上游淮河来水量的减少,驱动水体CO₂排放的因素逐渐由外源输入转变为水体有机质的呼吸降解.此外,上游河口区DOM中陆源类腐殖质的累积与矿化能够促进CO₂的排放,而内源有机质组分似乎并没有直接参与CO₂的排放过程.研究结果揭示了水文情景交替对湖库CO₂排放的重要影响,同时有必要进行高频观测以进一步明晰湖泊的碳通量变化及其控制因素.     

Sudden enhancement of sedimentation flux of <Superscript>210</Superscript>Pb<Subscript>ex</Subscript> as an indicator of lake productivity as exemplified by Lake Chenghai

The fundamental assumption of ²¹⁰Pb sediment dating is the stable flux of ²¹⁰Pb_ex, which was derived from atmosphere and then transferred into sediments via lake water. When the sedimentation rate is relatively constant, the ²¹⁰Pb_ex activity in sediments will be exponentially reduced with sedimentation age. ²¹⁰Pb_ex in lake water is incorporated into sediments mainly via organic particulates. If the sedimentation flux of organic matter in lake water is suddenly increased, ²¹⁰Pb_ex will be significantly deposited and then transferred into sediments. On the one hand such sudden purification effect is obviously unfit for the fundamental assumption of ²¹⁰Pb dating; on the other hand, the sudden enhancement of ²¹⁰Pb_ex flux would be indicative of the conspicuous variation of primary productivity of lake water. This problem will be discussed in accordance with the variation trend of ²¹⁰Pb_ex in the vertical profile of recent sediments of Lake Chenghai, Yunnan Province. The sediment core was collected from the deep-water area of Lake Chenghai in June 1997. The vertical profile of ¹³⁷Cs activity is characterized by a tree-peak pattern. This profile gave reliable ages, and also showed the stability of sediment accumulation in the recent ten years. The vertical profile of ²¹⁰Pb_ex activity displays a specific distribution of peaks, and is similar to the vertical profile of C_org. This phenomenon seems to be related to the mechanism of constraining the transfer of ²¹⁰Pb_ex into lake sediments. The average atomic ratios of H_org/C_org and C_org/N_org in Lake Chenghai sediments are 5.51 and 7.04, respectively, indicating that the organic matter was predominantly derived from the remains of endogenic algae. In terms of the three-stage evolutionary characteristics of organic matter in sediments, i.e., “deposition-de-composition-accumulation”, the sedimentation fluxes (F(C_org)) of organic carbon (C_org) since 1970 were calculated by modeling. The sedimentation fluxes of ²¹⁰Pb_ex (F(²¹⁰Pb_ex)) in different years display good synchronous relations with the sedimentation flux of organic carbon (F(C_org)), especially in the years of 1972–1974 and 1986–1989. The variation of F(C_org) led to the variation of F(²¹⁰Pb_ex); the variation of F(²¹⁰Pb_ex) reflects, to some extent, the historical variation of lake productivity.     

Net autotrophy in a fluvial lake: the relative role of phytoplankton and floating-leaved macrophytes

This study combined water- and sediment flux measurements with mass balances of dissolved gas and inorganic matter to determine the importance of pelagic and benthic processes for whole-system metabolism in a eutrophic fluvial lake. Mass balances of dissolved O₂, inorganic carbon (DIC), nitrogen (DIN), phosphorous (SRP), particulate N (PN) and P (PP) and Chl a were calculated at a nearly monthly frequency by means of repeated sampling at the lake inlet and outlet. Simultaneously, benthic fluxes of gas and nutrients, including denitrification rates, and the biomass of the dominant pleustophyte (Trapa natans) were measured, and fluxes of O₂ and CO₂ across the water–atmosphere interface were estimated from diel changes in outlet concentrations. On an annual scale, Middle Lake exhibited CO₂ supersaturation, averaging 313% (range 86–562%), but was autotrophic with a net O₂ production (6.35 ± 2.05 mol m⁻² y⁻¹), DIC consumption (−31.18 ± 18.77 mol m⁻² y⁻¹) and net export of Chl a downstream (8.38 ± 0.95 mol C m⁻² y⁻¹). Phytoplankton was the main driver of Middle Lake metabolism, with a net primary production estimated at 33.24 mol O₂ m⁻² y⁻¹, corresponding to a sequestration of 4.18 and 0.26 mol m⁻² y⁻¹ of N and P, respectively. At peak biomass, T. natans covered about 18% of Middle Lake’s surface and fixed 2.46, 0.17 and 0.02 mol m⁻² of C, N and P, respectively. Surficial sediments were a sink for O₂ (−14.47 ± 0.65 mol O₂ m⁻² y⁻¹) and a source of DIC and NH₄ ⁺ (18.84 ± 2.80 mol DIC m⁻² y⁻¹ and 0.83 ± 0.16 mol NH₄ ⁺ m⁻² y⁻¹), and dissipated nitrate via denitrification (1.44 ± 0.11 mol NO₃ ⁻ m⁻² y⁻¹). Overall, nutrient uptake by primary producers and regeneration from sediments were a minor fraction of external loads. This work suggests that the creation of fluvial lakes can produce net autotrophic systems, with elevated rates of phytoplanktonic primary production, largely sustained by allochtonous nutrient inputs. These hypereutrophic aquatic bodies are net C sinks, although they simultaneously release CO₂ to the atmosphere.     

Gas emissions from failed and actual eruptions from Cook Inlet Volcanoes,Alaska, 1989–2006

Cook Inlet volcanoes that experienced an eruption between 1989 and 2006 had mean gas emission rates that were roughly an order of magnitude higher than at volcanoes where unrest stalled. For the six events studied, mean emission rates for eruptions were ∼13,000 t/d CO₂ and 5200 t/d SO₂, but only ∼1200 t/d CO₂ and 500 t/d SO₂ for non-eruptive events (‘failed eruptions’). Statistical analysis suggests degassing thresholds for eruption on the order of 1500 and 1000 t/d for CO₂ and SO₂, respectively. Emission rates greater than 4000 and 2000 t/d for CO₂ and SO₂, respectively, almost exclusively resulted during eruptive events (the only exception being two measurements at Fourpeaked). While this analysis could suggest that unerupted magmas have lower pre-eruptive volatile contents, we favor the explanations that either the amount of magma feeding actual eruptions is larger than that driving failed eruptions, or that magmas from failed eruptions experience less decompression such that the majority of H₂O remains dissolved and thus insufficient permeability is produced to release the trapped volatile phase (or both). In the majority of unrest and eruption sequences, increases in CO₂ emission relative to SO₂ emission were observed early in the sequence. With time, all events converged to a common molar value of C/S between 0.5 and 2. These geochemical trends argue for roughly similar decompression histories until shallow levels are reached beneath the edifice (i.e., from 20–35 to ∼4–6 km) and perhaps roughly similar initial volatile contents in all cases. Early elevated CO₂ levels that we find at these high-latitude, andesitic arc volcanoes have also been observed at mid-latitude, relatively snow-free, basaltic volcanoes such as Stromboli and Etna. Typically such patterns are attributed to injection and decompression of deep (CO₂-rich) magma into a shallower chamber and open system degassing prior to eruption. Here we argue that the C/S trends probably represent tapping of vapor-saturated regions with high C/S, and then gradual degassing of remaining dissolved volatiles as the magma progresses toward the surface. At these volcanoes, however, C/S is often accentuated due to early preferential scrubbing of sulfur gases. The range of equilibrium degassing is consistent with the bulk degassing of a magma with initial CO₂ and S of 0.6 and 0.2 wt.%, respectively, similar to what has been suggested for primitive Redoubt magmas.