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.     

Estimating thermal inflow to El Chichón crater lake using the energy-budget,chemical and isotope balance approaches

El Chichón crater lake appeared immediately after the 1982 catastrophic eruption in a newly formed, 1-km wide, explosive crater. During the first 2 years after the eruption the lake transformed from hot and ultra-acidic caused by dissolution of magmatic gases, to a warm and less acidic lake due to a rapid “magmatic-to-hydrothermal transition” — input of hydrothermal fluids and oxidation of H₂S to sulfate. Chemical composition of the lake water and other thermal fluids discharging in the crater, stable isotope composition (δD and δ¹⁸O) of lake water, gas condensates and thermal waters collected in 1995–2006 were used for the mass-balance calculations (Cl, SO₄ and isotopic composition) of the thermal flux from the crater floor. The calculated fluxes of thermal fluid by different mass-balance approaches become of the same order of magnitude as those derived from the energy-budget model if values of 1.9 and 2 mmol/mol are taken for the catchment coefficient and the average H₂S concentration in the hydrothermal vapors, respectively. The total heat power from the crater is estimated to be between 35 and 60 MW and the CO₂ flux is not higher than 150 t/day or ~ 200 gm^− 2 day^− 1.     

D/H and O/O ratios of water in the crater lake at Kusatsu-Shirane volcano, Japan

The D/H and ¹⁸O/¹⁶O ratios of water in the active crater lake situated on the Kusatsu-Shirane volcano, Japan are about 20 and 6‰, respectively, higher than local meteoric water. The ratios show seasonal variations superimposed on a gradual change over nine years. The isotopic ratios started to increase in early 1990 and decrease in the spring of 1995. The seasonal variation which is high in winter and low in summer correlates with the temperature difference between lake water and ambient air. The large temperature difference in winter enhances the evaporation of lake water and produces the enriched isotopic ratios relative to the ratios in summer. The accumulation of snow and the decrease in the flux of meteoric water into the lake strengthens the winter-time isotopic enrichment. The enriched isotopic ratios of the lake water over a long time result from the addition of an end member with heavy isotopic ratios contained in a thermal fluid supplied to the lake. Considering the water balance in the lake, the isotopic ratios of the thermal fluid were found to be close to the lake water itself, suggesting the circulation of the lake water seeping through lake floor. Based on the correlation between Cl⁻concentration and the isotopic ratios, the contribution by the heavy end member was estimated to be 25–36% relative to the enrichment by evaporation. The heavy end member could be a liquid phase evolved from a parental fluid, which is a mixture of local meteoric water and a magmatic fluid as found in high-temperature volcanic gases.     

Sulfur isotopic effects in the disproportionation reaction of sulfur dioxide in hydrothermal fluids: implications for the δS variations of dissolved bisulfate and elemental sulfur from active crater lakes

Sulfur isotope effects during the SO₂ disproportionation reaction to form elemental sulfur (3SO₂+3H₂O→2HSO₄⁻+S+2H⁺) at 200–330°C and saturated water vapor pressures were experimentally determined. Initially, a large kinetic isotopic fractionation takes place between HSO₄⁻ and S, followed by a slow approach to equilibrium. The equilibrium fractionation factors, estimated from the longest run results, are expressed by 1000 ln α_HSO4⁻–S=6.21×10⁶/T²+3.62. The rates at which the initial kinetic fractionation factors approach the equilibrium ones were evaluated at the experimental conditions.δ³⁴S values of HSO₄⁻ and elemental sulfur were examined for active crater lakes including Noboribetsu and Niseko, (Hokkaido, Japan), Khloridnoe, Bannoe and Maly Semiachik (Kamchatka), Poás (Costa Rica), Ruapehu (New Zealand) and Kawah Ijen and Keli Mutu (Indonesia). Δ_HSO4⁻–S values are 28‰ for Keli Mutu, 26‰ for Kawah Ijen, 24‰ for Ruapehu, 23‰ for Poás, 22‰ for Maly Semiachik, 21‰ for Yugama, 13‰ for Bannoe, 9‰ for Niseko, 4‰ for Khloridonoe, and 0‰ for Noboribetsu, in the decreasing order. The SO₂ disproportionation reaction in the magmatic hydrothermal system below crater lakes where magmatic gases condense is responsible for high Δ_HSO4⁻–S values, whereas contribution of HSO₄⁻ produced through bacterial oxidation of reduced sulfur becomes progressively dominant for lakes with lower Δ_HSO4⁻–S values. Currently, Noboribetsu crater lake contains no HSO₄⁻ of magmatic origin. A 40-year period observation of δ³⁴S_HSO4⁻ and δ³⁴S_S values at Yugama indicated that the isotopic variations reflect changes in the supply rate of SO₂ to the magmatic hydrothermal system. This implies a possibility of volcano monitoring by continuous observation of δ³⁴S_HSO4⁻ values. The δ¹⁸O values of HSO₄⁻ and lake water from the studied lakes covary, indicating oxygen isotopic equilibration between them. The covariance gives strong evidence that lake water circulates through the sublimnic zone at temperatures of 140±30°C.     

Temporal changes in the chemistry of lake water within Yugama Crater,Kusatsu-Shirane Volcano,Japan: Implications for the evolution of the magmatic hydrothermal system

The chemical composition and temperature of lake water within Yugama Crater, Kusatsu-Shirane Volcano, Japan, have fluctuated markedly over the period 1966 to 2005. From 1966 to 1981, water temperature was relatively low, and Cl⁻ and SO₄²⁻ concentrations gradually decreased. These trends are explained by the growth of a sealing zone that formed between the region of hot rock surrounding the degassing magma and cool crust saturated with groundwater. The sealing zone acted to restrict the emission of magmatic volatiles.     

巢湖杭埠河流域湖相沉积物多指标揭示的全新世以来环境演变

在巢湖杭埠河流域中的古湖盆中心——三河圩区获取28.6 m长的湖相岩芯（SZK1507孔）,利用AMS¹⁴C测年技术建立可靠的地层年代序列,通过对SZK1507孔738 cm以上段湖相沉积物平均粒径、磁化率、总氮（TN）、总有机碳（TOC）及C/N的综合分析,高分辨率重建了巢湖杭埠河流域全新世以来的古环境演变过程.结果表明,本区域的环境变化过程可以分为4个阶段,阶段Ⅰ（约10050—9700 cal.a B.P.）与阶段Ⅲ（约9250—5300 cal.a B.P.）气候较为湿润,巢湖水位较高,平均粒径、磁化率值较低,TN、TOC、C/N也偏低;阶段Ⅱ（约9700—9250 cal.a B.P.）与阶段Ⅳ（约5300 cal.a B.P.以来）气候干燥,巢湖水量减少,水位降低,平均粒径、磁化率值、TN、TOC、C/N均较高.一些全球范围内显著发生的气候突变事件在SZK1507孔沉积记录中也有体现,如9.3、8.2和4.2 ka B.P.事件等.将巢湖杭埠河流域10000 cal.a B.P.以来的平均粒径、磁化率、TN、TOC、C/N沉积记录与全新世以来的北纬30°夏季太阳辐射量、太阳黑子数、火山喷发对大气中硫酸盐含量贡献率等进行对比,发现巢湖杭埠河流域全新世气候突变事件主要受控于北半球夏季太阳辐射量变化、太阳活动以及火山活动等因素,并与它们之间复杂的响应机制有关.     

Environmental changes reflected by the lake sediments of the South Hongshan Lake, Northwest Tibet

The 1.07-m long lake core with 1 cm interval cutting, which was obtained by drilling in the South Hongshan Lake of Northwest Tibet, was dated by the 210Pb and 137Cs methods, and a 150-year consecutive lake sedimentary sequence (1840─1997) with 1.4 year resolution was obtained. Some environmental proxies, such as the total organic carbon (TOC), total nitrogen (TN), ratio of TOC to TN (TOC/TN), trace chemistry elements (TCE), CaCO3, grain size, richness of ostracoda etc. showed that they are of well coincidence. These results implied that the environmental background varied from the cold-wet period in the late 19th century, to the warm-wet period from the end of the 19th century to the 1920s and to the warm-dry period since the 1920s. There were sub-variations since the 1920s: the cold-dry/warm-wet fluctuation from 1922 to 1960, the intensively warm-dry period since 1960 with a short cold-wet period in the mid-1970s to the end of the 1980s. The humid period from the mid-1970s to the end of the 1970s and the dry period beginning from the early 1980s were well documented by climatic data of the nearby weather station records while the grain size was well correlated to the annual precipitation. Compared with the records from Guliya ice core in the same area, the TOC proxy in the lake core indicating warm/cold conditions well corresponded to the ( 18O records representing temperature variations in the ice core. However, the proxies with dry/wet significance in the lake core were different from the variations of snow accumulation reflected by the ice core. It can be concluded that the chosen environmental proxies have clear environmental significance and the lake sediments can reflect climatic and environmental changes at high-resolution.     

Implications for eruptive processes as indicated by sulfur dioxide emissions from K lauea Volcano, Hawai‘i, 1979–1997

K lauea Volcano, Hawai‘i, currently hosts the longest running SO₂ emission-rate data set on the planet, starting with initial surveys done in 1975 by Stoiber and his colleagues. The 17.5-year record of summit emissions, starting in 1979, shows the effects of summit and east rift eruptive processes, which define seven distinctly different periods of SO₂ release. Summit emissions jumped nearly 40% with the onset (3 January 1983) of the Pu‘u ‘ ‘ -K paianaha eruption on the east rift zone (ERZ). Summit SO₂ emissions from K lauea showed a strong positive correlation with short-period, shallow, caldera events, rather than with long-period seismicity as in more silicious systems. This correlation suggests a maturation process in the summit magma-transport system from 1986 through 1993. During a steady-state throughput-equilibrium interval of the summit magma reservoir, integration of summit-caldera and ERZ SO₂ emissions reveals an undegassed volume rate of effusion of 2.1×10⁵ m³/d. This value corroborates the volume-rate determined by geophysical methods, demonstrating that, for K lauea, SO₂ emission rates can be used to monitor effusion rate, supporting and supplementing other, more established geophysical methods. For the 17.5 years of continuous emission rate records at K lauea, the volcano has released 9.7×10⁶ t (metric tonnes) of SO₂, 1.7×10⁶ t from the summit and 8.0×10⁶ t from the east rift zone. On an annual basis, the average SO₂ release from K lauea is 4.6×10⁵ t/y, compared to the global annual volcanic emission rate of 1.2×10⁷ t/y.     

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.     

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.     

水位变化对干涸湖底沉积物有机碳矿化的影响

人为干扰和气候变化会改变湖泊水位状态,明确不同水位条件下湖泊沉积物有机碳矿化特征及其影响因素,对了解内陆水生态系统碳循环具有重要意义.为探究干旱区典型盐湖沉积物有机碳矿化速率对水位变化的响应,以巴里坤湖干涸湖底原状沉积物为研究对象,初步探究了0（T1）、-9（T2）、-23（T3）、-34（T4）和-45 cm（T5）水位处理对沉积物有机碳矿化速率的影响.结果表明,T1、T2和T3处理有机碳矿化速率在试验初期较高（0~10 d）,10 d后缓慢下降,T4和T5处理有机碳矿化速率呈先增加后降低趋势;T1（1.718 μmol/（m²·s））与T3（1.784 μmol/（m²·s））处理有机碳矿化速率不存在显著差异,T1处理有机碳矿化速率是T2、T4和T5处理的1.09、3.31和3.57倍,不同处理有机碳累积矿化量表现为T3 > T1 > T2 > T4 > T5.有机碳累积矿化量（C_t）占沉积物有机碳（C₀）的比例（C_t/C₀）介于0.012~0.044之间,沉积物有机碳潜在排放量（C_i）占C₀的比例（C_i/C₀）介于0.018~0.045之间;水位降低,沉积物有机碳矿化常数（k值）减小,T1处理k值最大（0.137 d）,T4处理最小（0.032 d）.线性方程C_r=0.008x+0.488能较好地模拟有机碳矿化速率（C_r）与水位（x）的关系;不同水位处理有机碳矿化速率与模拟柱中沉积物5 cm温度呈显著的指数函数关系,T4、T5处理有机碳矿化温度敏感系数（Q₁₀）显著高于T1、T2和T3处理,即水位降低增加了巴里坤湖干涸湖底沉积物Q₁₀.因此,就巴里坤湖干涸湖底沉积物而言,水位从0 cm降至-45 cm时有机碳矿化速率降低,Q₁₀增加;反之水位上升则会促进有机碳矿化分解,Q₁₀降低.水位持续下降抑制有机碳矿化可能是维持干旱区盐湖沉积物碳库稳定的机制之一.     

Monitoring Quiescent Volcanoes by Diffuse CO2 Degassing: Case Study of Mt. Fuji, Japan

Since the 8th century, more than seventeen eruptions have been recorded for the Mt. Fuji volcano, with the most recent eruption occurring in 1707 (Hoei eruption). For the past 300 years the volcano has been in a quiescent stage and, since the early 1960s, has exhibited neither fumarolic nor thermal activity. However, the number of low-frequency earthquakes with a hypocentral depth of 10–20 km increased significantly beneath the northeastern flank of Mt. Fuji in 2000–2001, suggesting a possible resumption of magmatic activity. In this study, diffuse CO₂ efflux and thermal surveys were carried out in four areas of the volcano in 2001–2002 in order to detect possible signs of the upward movement of deep magma. At all survey points, the CO₂ efflux was below the detection limit with the exception of a few points with biological CO₂ emission, and ground temperatures at a depth of 20–30 cm were below ambient, indicating no surface manifestations of gas or heat emission. Should magma rise into the subsurface, the diffuse CO₂ efflux would be expected to increase, particularly along the tectonically weakened lineation on the Mt. Fuji volcano, allowing for the early detection of pre-eruptive degassing.     

Onshore-offshore gradient in reductive early diagenesis in coastal marine sediments of the Ria de Vigo, Northwest Iberian Peninsula

Early diagenetic modification of magnetic properties is an important process in marine sediments, but temporal and spatial variability of diagenetic processes have rarely been reported for recent coastal sediments. The magnetic properties of sediments from the Ria de Vigo (NW Spain) define a marked three-part zonation with depth. The uppermost zone is magnetically dominated by (titano-)magnetite. In the intermediate zone, rapid down-core dissolution of (titano-)magnetite increases the relative influence of high-coercivity magnetic minerals, which react more slowly during reductive dissolution than (titano-)magnetite. This zone is characterized by the ubiquitous occurrence of framboidal iron sulphides. Pyrite is the dominant iron sulphide, but framboidal ferrimagnetic greigite is also frequently observed in association with pyrite. The lowermost zone is characterized by an almost complete depletion of magnetic minerals associated with progressive reduction of detrital iron oxides with depth. This zonation is controlled by organic matter diagenesis, which varies with water depth and wave-induced sediment resuspension and organic matter reoxidation in the water column. This leads to a shallowing and thinning of each zone with more intense reductive diagenesis toward the interior of the ria. Such a zonation seems to be a common feature in shallow water marine environments. If preserved, the described zonation and its spatial variability provide a potential tool for detecting estuarine-like environments in the geological record. Magnetic detection of current or past reductive conditions also has important implications for assessing paleoenvironmental proxies that are sensitive to diagenetic redox state.     

抚仙湖沉积物多指标记录的过去5000年湖泊环境变化

我国西南地区湖泊众多,利用湖泊沉积物已开展了大量全新世植被、降水、温度和水位等的重建工作.然而,代用指标的季节性差异和气候演变的区域差异使得不同代用指标和地区重建的古气候结果存在较大差异,需要更多可靠记录来相互佐证和构建我国西南地区气候变化的详细图景.本文以云南抚仙湖FXH-6钻孔沉积物为研究对象,对正构烷烃和色度指标作了分析,在厘清其来源及环境指示意义的基础上,重建过去近5000年抚仙湖有机质的来源和湖泊水位的变化,探讨了湖泊环境变化与区域气候变化的关系.结果表明,抚仙湖沉积物中正构烷烃n-C₂₃和n-C₃₁可有效指示内源沉水植物和外源陆生植物.近5000年抚仙湖湖泊环境经历了3个阶段:在5000—2300 cal a BP阶段,沉水植物广泛分布,湖泊水位处于高位;在2300—2000 cal a BP阶段,抚仙湖沉积环境快速变化,内源沉水植物生物量锐减,水位快速下降;2000 cal a BP至今,沉水植物生物量持续减少,湖泊水位保持低水位;同时,人类活动也影响了该阶段(2000 cal a BP至今)陆源植物的输入.本研究重建的抚仙湖持续降低的水位变化和湖泊生产力趋势与过去5000年西南地区的年平均温逐渐降低、年平均降水量逐渐减小的总体趋势相对应,表明区域气候变化是湖泊沉积环境变化的主要驱动力.