Geochemistry of the magmatic–hydrothermal system of Kawah Ijen volcano, East Java, Indonesia

Samples from Kawah Ijen crater lake, spring and fumarole discharges were collected between 1990 and 1996 for chemical and isotopic analysis. An extremely low pH (<0.3) lake contains SO₄–Cl waters produced during absorption of magmatic volatiles into shallow ground water. The acidic waters dissolve the rock isochemically to produce “immature” solutions. The strong D and ¹⁸O enrichment of the lake is mainly due to enhanced evaporation at elevated temperature, but involvement of a magmatic component with heavy isotopic ratios also modifies the lake D and ¹⁸O content. The large Δ_SO4–S⁰ (23.8–26.4‰) measured in the lake suggest that dissolved SO₄ forms during disproportionation of magmatic SO₂ in the hydrothermal conduit at temperatures of 250280°C. The lake δ¹⁸O_SO4 and δ¹⁸O_H2O values may reflect equilibration during subsurface circulation of the water at temperatures near 150°C. Significant variations in the lake's bulk composition from 1990 to 1996 were not detected. However, we interpret a change in the distribution and concentration of polythionate species in 1996 as a result of increased SO₂-rich gas input to the lake system.Thermal springs at Kawah Ijen consist of acidic SO₄–Cl waters on the lakeshore and neutral pH HCO₃–SO₄–Cl–Na waters in Blawan village, 17 km from the crater. The cation contents of these discharges are diluted compared to the crater lake but still do not represent equilibrium with the rock. The SO₄/Cl ratios and water and sulfur isotopic compositions support the idea that these springs are mixtures of summit acidic SO₄–Cl water and ground water.The lakeshore fumarole discharges (T=170245°C) have both a magmatic and a hydrothermal component and are supersaturated with respect to elemental sulfur. The apparent equilibrium temperature of the gas is 260°C. The proportions of the oxidized, SO₂-dominated magmatic vapor and of the reduced, H₂S-dominated hydrothermal vapor in the fumaroles varied between 1979 and 1996. This may be the result of interaction of SO₂-bearing magmatic vapors with the summit acidic hydrothermal reservoir. This idea is supported by the lower H₂S/SO₂ ratio deduced for the gas producing the SO₄–Cl reservoir feeding the lake compared with that observed in the subaerial gas discharges. The condensing gas may have equilibrated in a liquid–vapor zone at about 350°C.Elemental sulfur occurs in the crater lake environment as banded sediments exposed on the lakeshore and as a subaqueous molten body on the crater floor. The sediments were precipitated in the past during inorganic oxidation of H₂S in the lake water. This process was not continuous, but was interrupted by periods of massive silica (poorly crystallized) precipitation, similar to the present-day lake conditions. We suggest that the factor controlling the type of deposition is related to whether H₂S- or silica-rich volcanic discharges enter the lake. This could depend on the efficiency with which the lake water circulates in the hydrothermal cell beneath the crater. Quenched liquid sulfur products show δ³⁴S values similar to those found in the banded deposits, suggesting that the subaqueous molten body simply consists of melted sediments previously accumulated at the lake bottom.     

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.     

Geochemistry of the acid Kawah Putih lake, Patuha Volcano, West Java, Indonesia

Kawah Putih is a summit crater of Patuha volcano, West Java, Indonesia, which contains a shallow, 300 m-wide lake with strongly mineralized acid–sulfate–chloride water. The lake water has a temperature of 26–34°C, pH=<0.5–1.3, S^tot=2500–4600 ppm and Cl=5300–12 600 ppm, and floating sulfur globules with sulfide inclusions are common. Sulfur oxyanion concentrations are unusually high, with S₄O₆²⁻+S₅O₆²⁻+S₆O₆²⁻=2400 – 4200 ppm. Subaerial fumaroles (<93°C) on the lake shore have low molar SO₂/H₂S ratios (<2), which is a favorable condition to produce the observed distribution of sulfur oxyanion species. Sulfur isotope data of dissolved sulfate and native sulfur show a significant ³⁴S fractionation (ΔSO₄–S_e of 20‰), probably the result of SO₂ disproportionation in or below the lake. The lake waters show strong enrichments in ¹⁸O and D relative to local meteoric waters, a result of the combined effects of mixing between isotopically heavy fluids of deep origin and meteoric water, and evaporation-induced fractionation at the lake surface. The stable-isotope systematics combined with energy-balance considerations support very rapid fluid cycling through the lake system. Lake levels and element concentrations show strong seasonal fluctuations, indicative of a short water residence time in the lake as well.Thermodynamic modeling of the lake fluids indicates that the lake water is saturated with silica phases, barite, pyrite and various Pb, Sb, Cu, As, Bi-bearing sulfides when sulfur saturation is assumed. Precipitating phases predicted by the model calculations are consistent with the bulk chemistry of the sulfur-rich bottom sediments and their identified mineral phases. Much of the lake water chemistry can be explained by congruent rock dissolution in combination with preferential enrichments from entering fumarolic gases or brines and element removal by precipitating mineral phases, as indicated by a comparison of the fluids, volcanic rocks and lake bed sediment.Flank springs on the mountain at different elevations vary in composition, and are consistent with local rock dissolution as a dominant factor and pH-dependent element mobility. Discharges of warm sulfate- and chloride-rich water at the highest elevation and a near-neutral spring at lower level may contain a small contribution of crater-lake water. The acid fluid-induced processes at Patuha have led to the accumulation of elements that are commonly associated with volcano-hosted epithermal ore deposits. The dispersal of heavy metals and other potentially toxic elements from the volcano via the local drainage system is a matter of serious environmental concern.     

A stable isotope study of the Garda lake, northern Italy: Its hydrological balance

Discontinuous measurements of the isotopic composition of surface water samples of the Garda lake carried out between 1998 and 2006 showed almost constant δ¹⁸O, δD and d-excess values through time. During 2006 and 2007 monthly vertical profiles of water samples were collected in the northernmost section of the lake, not far from the main inflow (Sarca river) to check whether there was any detectable influence from this inflowing river and whether there was a vertical isotopic stratification of the lake water. The isotopic measurement of water samples from the vertical profiles yielded isotopic values which were almost equal to those obtained from surface waters showing no detectable effect of the inflowing river water and no isotopic vertical stratification. The attempt to evaluate the evaporation rate of lake water by means of current models was totally unsuccessful. Despite the marked summer warming of the surface layer no isotopic fractionation related to evaporation processes could be detected. This anomalous behaviour may be related to the large amount of spring and summer precipitation characteristic of this area. The water balance of the lake calculated according to the amount of the inflowing water (Sarca river water plus rain water on the lake plus 20% of the precipitations on the whole catchment basin) and to the amount of outflowing water (Mincio river) showed a large imbalance, the river outflow alone resulting on average, during the last decade, at least double the inflow. To explain this imbalance of the lake, a large recharge by concealed groundwater is suggested: its isotopic composition should be quite close to the mean isotopic composition of precipitations over that area. This would be in agreement with the almost constant isotopic composition of both surface and deep waters and with the lack of vertical isotopic stratification. A few measurements of the tritium concentration carried out on lake water show values that are considerably higher than modern tritium values either in precipitation or in the Sarca river water: these results are in good agreement with the hypothesis of a recharge of the lake by deep aquifers.     

The stable isotope geochemistry of volcanic lakes, with examples from Indonesia

Stable isotope compositions (δD, δ¹⁸O and δ³⁴S) of volcanic lake waters, gas condensates and spring waters from Indonesia, Italy, Japan, and Russia were measured. The spring fluids and gas samples plot in a broad array between meteoric waters and local high-temperature volcanic gas compositions. The δD and δ¹⁸O data from volcanic lakes in East Indonesia plot in a concave band ranging from local meteoric waters to evaporated fluids to waters heavier than local high-temperature volcanic gases. We investigated isotopic fractionation processes in volcanic lakes at elevated temperatures with simultaneous mixing of meteoric waters and volcanic gases. An elevated lake water temperature gives enhanced kinetic isotope fractionation and changes in equilibrium fractionation factors, providing relatively flat isotope evolution curves in δ¹⁸O–δD diagrams. A numerical simulation model is used to derive the timescales of isotopic evolution of crater lakes as a function of atmospheric parameters, lake water temperature and fluxes of meteoric water, volcanic gas input, evaporation, and seepage losses. The same model is used to derive the flux magnitude of the Keli Mutu lakes in Indonesia. The calculated volcanic gas fluxes are of the same order as those derived from energy budget models or direct gas flux measurements in open craters (several 100 m³ volcanic water/day) and indicate a water residence time of 1–2 decades. The δ³⁴S data from the Keli Mutu lakes show a much wider range than those from gases and springs, which is probably related to the precipitation of sulfur in these acid brine lakes. The isotopic mass balance and S/Cl values suggest that about half of the sulfur input in the hottest Keli Mutu lake is converted into native sulfur.     

The volcanic acidification of glacial Lake Caviahue,Province of Neuquen,Argentina

Lake Caviahue (northern Patagonia, Argentina) is a large glacial lake acidified by volcanic fluids from Copahue volcano. The lake and the feeding rivers were sampled annually from 1997 till early 2006, including the eruptive period of 2000. Lake Caviahue waters evolved over time, with the most concentrated waters in 2000 during the eruptive period, followed by gradual dilution that was interrupted by renewed acidification in 2003–2004. Inversion of the lake water data and application of a dynamic non-steady state model for the lake provides our best quantitative estimates for the variation in element fluxes over the 9-year period. The model flux results agree well with most of the measured fluxes. The Copahue hydrothermal system had gently declining element fluxes between 1997 and mid-1999, although the lake was still becoming more concentrated. About 2–3 months before the 2000 eruption, element fluxes increased strongly, but the hydrothermal fluxes almost shutoff directly after the main eruptive events. The fluxes of several elements recovered post-2001, with an increase in element fluxes in 2003–2004; the lake became more dilute between 2004 and 2006. The intrusion of new magma into the hydrothermal system just prior to the 2000 eruption led to enhanced water rock interaction, with higher concentrations of the rock forming elements in the fluids, and the hot spring flow rate increased as a result of the higher pressure in the reservoir. The fluids became saturated in alunite and jarosite, and they were already saturated with anhydrite. Precipitation of these minerals possibly led to a decreased permeability of the hydrothermal reservoir, leading to the strongly reduced element fluxes just after the eruption. In addition, K, Al and S were retained in the newly precipitated minerals as well, further diminishing their export. The acidification in 2003–2004 may have resulted from a new small intrusion of magma or resulted from seismic activity that created new permeability and fresh rock surfaces for water rock interaction. The volcano is a significant source of toxic trace elements such as F, As, B and Li as well as a nutrient (P) for the local watershed. Monitoring of the hydrothermal fluids in the river that drains Copahue, especially the S/Cl, Mg/Cl and Mg/K values as well as the magnitude of the element fluxes would provide the best information for eruption forecasting for this volcano.     

Lithium isotope variations in Tonga–Kermadec arc–Lau back‐arc lavas and Deep Sea Drilling Project (DSDP) Site 204 sediments

Lithium isotopes have been identified as a promising tracer of subducted materials in arc lavas due to the observable variations in related reservoirs such as subducting sediments and altered oceanic crust. The Tonga–Kermadec arc–Lau back‐arc provides an end‐member of subduction zones with the coldest thermal structure on Earth. Reported here are Li isotope data for 14 lavas from the arc front and 7 back‐arc lavas as well as 12 pelagic and volcaniclastic sediments along a profile through the sedimentary sequence at DSDP Site 204. The arc and back‐arc lavas range from basalts to dacites in composition with SiO₂ = 48.3–65.3 wt% over which Li concentrations increase from 2 ppm to 16 ppm. Li/Y ratios range from 0.08 to 0.77 and from 0.24 to 0.65 in the arc and back‐arc lavas, respectively. The majority of the lavas have δ⁷Li that ranges from 2.5 ‰ to 5.0 ‰ with an average of (3.6 ±0.7) ‰, similar to that reported from other arcs and there is no distinction between the arc front and back‐arc lavas. The pelagic sediments have variable Li concentrations (33–133 ppm) and δ⁷Li that ranges from 1.2 ‰ to 10.2 ‰ while the volcaniclastic sediments have an even greater range of Li concentrations (3.6–165 ppm) and generally higher δ⁷Li values (8–14 ‰). However, δ⁷Li in the lavas does not correlate with commonly used trace element ratio or isotope signatures indicative of slab‐derived fluids or the sediments. This is probably because the range of δ⁷Li in the lavas and sediments overlap. Calculated sediment mass‐balance models require significantly more sediment than previous estimates based on Th–Nd–Be isotopes. This may indicate that a sizeable proportion of the total Li budget in the lavas is provided by Li‐enriched fluids from the subducting sediments and/or altered oceanic crust.     

Dual effects of precipitation and evaporation on lake water stable isotope composition in the monsoon region

We present the results of a 3‐year monitoring programme of the stable isotope composition of lake water and precipitation at Taozi Lake, in the East Asian monsoon region of China. Our aims were to reveal the spatiotemporal pattern of variation of stable isotopes in a small closed‐basin lake and to quantitatively determine the impacts of precipitation and evaporation on the stable isotope composition of lake water under a humid monsoon climate. In the time domain, the stable oxygen isotopic ratio of the lake water (δ¹⁸O_L) exhibited substantial seasonal and interannual variations, but the isotope variations between different precipitation events substantially exceeded seasonal and interannual variations. Compared with the stable isotopes in precipitation, δ¹⁸O_L was substantially positive and d_L was negative. In the space domains, the lake water was homogeneously mixed. Indicated by statistic analyses, precipitation plays a dominant role in dynamic of the lake stable isotope during precipitation events of relatively large magnitude, whereas the effect of evaporation is dominant during smaller precipitation events. Results advance our understanding of the stable isotope change rule in the process of lake water evaporation, and it is helpful to identify the climatic significance recorded in stable isotopic compositions of lake bottom sediments.     

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.     

Characteristics of δ13CDIC in lakes on the Tibetan Plateau and its implications for the carbon cycle

Dissolved inorganic carbon isotope (δ¹³C_DIC) is an important tool to reveal the carbon cycle in lake systems. However, there are only few studies focusing on the spatial variation of δ¹³C_DIC of closed lakes. Here we analyze the characteristics of δ¹³C_DIC of 24 sampled lakes (mainly closed lakes) across the Qiangtang Plateau (QTP) and identify the driving factors for its spatial variation. The δ¹³C_DIC value of these observed lakes varies in the range of ? 15·0 to 3·2‰, with an average value of ? 1·2‰. The δ¹³C_DIC value of closed lakes is close to the atmospheric isotopic equilibrium value, much higher than that in rivers and freshwater lakes reported before. The high δ¹³C_DIC value of closed lakes is mainly attributed to the significant contribution of carbonate weathering in the catchment and the evasion of dissolved CO₂ induced by the strong evaporation of lake water. The δ¹³C_DIC value of closed lakes has a logarithmic correlation with water chemistry (TDS, DIC and pCO₂), also suggesting that the evapo‐concentration of lake water can influence the δ¹³C_DIC value. The δ¹³C_DIC value shows two opposite logarithmic correlations with lake size depending on the δ¹³C_DIC range. This study suggests that the δ¹³C in carbonates in lacustrine sediments can be taken as an indicator of lake volume variation in closed lakes on QTP. Copyright © 2011 John Wiley & Sons, Ltd.     

Hydrogeological and hydrogeochemical control of groundwater salinity in an arid inland basin: Dunhuang Basin,northwestern China

High groundwater salinity has become a major concern in the arid alluvial plain of the Dunhuang Basin in northwestern China because it poses a significant challenge to water resource management. Isotopic and geochemical analyses were conducted on 55 water samples from springs, boreholes and surface water to identify potential sources of groundwater salinity and analyse the processes that control increasing salinity. The total dissolved solid (TDS) content in the groundwater ranged from 400 to 41 000 mg/l, and high TDS values were commonly associated with shallow water tables and flow‐through and discharge zones in unconfined aquifers. Various groundwater contributions from rainwater, agricultural irrigation, river water infiltration and lateral inflows from mountains were identified by major ions and δD and δ¹⁸O. In general, HCO₃^? and SO₄^2? were the dominant anions in groundwater with a salinity of <2500 mg/l, whereas Cl^? and SO₄^2? were the dominant anions in groundwater with a salinity of >2500 mg/l. The major ion concentrations indicated that mineral weathering, including carbonate and evaporite dissolution, primarily affected groundwater salinity in recharge areas. Evapotranspiration controlled the major ion concentration evolution and salinity distribution in the unconfined groundwaters in the flow‐through and discharge areas, although it had a limited effect on groundwater in the recharge areas and confined aquifers. Agricultural irrigation increased the water table and enhanced evapotranspiration in the oasis areas of the basin. TDS and Cl became more concentrated, but H and O isotopes were not enriched in the irrigation district, indicating that transpiration dominated the increasing salinity. For other places in the basin, as indicated by TDS, Cl, δD and δ¹⁸O characteristics, evaporation, transpiration and water–rock interactions dominated at different hydrogeological zones, depending on the plant coverage and hydrogeological conditions. Groundwater ages of ³H, and δD and δ¹⁸O compositions and distributions suggest that most of the groundwaters in Dunhuang Basin have a paleometeoric origin and experienced a long residence time. These results can contribute to groundwater management and future water allocation programmes in the Dunhuang Basin. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

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     

Chemistry of the crater lake during the 1971–1972 Soufrière eruption

During the 1971–1972 eruption of Soufrière volcano on St. Vincent Island, a lava mass was extruded subaqueously in the crater lake. An investigation of the chemistry of the lake indicates that over 50,000 tons of dissolved solids were taken into solution during the eruption, in addition to 9000 tons of iron precipitated as ferric oxide in syngenetic metalliferous sediments on the crater floor. Leaching of hot disintegrating lava and volcanic glass is the principal source of cations dissolved in the lake (Na, Ca, Mg, Si and K), whereas chlorine and sulfur were introduced during injection of acid volcanic gases from the submerged lava mass. Concentrations of the common cations in the lake are not affected by mineral solubility, except in the case of Fe³⁺, but rather by the rate of leaching, evaporation, and water-rock reactions. Variations in Cl/Na, total Cl and acidity have aided in identification of distinct fumarolic phases during the eruption, which may correlate with observed increase in frequency of minor volcanic tremors in the crater. Accumulation of ferric oxide in sediments on the crater floor is thought to be due to leaching of ferrous iron at high temperature from the lava mass, followed by oxidation and precipitation of hematite in the cooler lake.     

Downstream composition changes of acidic volcanic waters discharged into the Banyupahit stream, Ijen caldera, Indonesia

The crater lake of Kawah Ijen volcano contains extremely low pH (<0.4) waters with high SO₄ (70000 mg/kg), Cl (21000 mg/kg), F (1500 mg/kg), Al (5000 mg/kg), Fe (2000 mg/kg) and trace metal (Cu 0.5, Zn 4, Pb 3 mg/kg) contents. These brines seep outward through the western crater rim and reappear on the other side as streamlets, which form the headwaters of the Banyupahit stream. The Banyupahit first mixes with fresh rivers and thermal springs in the Ijen caldera and then irrigates a coastal agricultural plain which is 30 km from the summit crater.We discuss the downstream composition changes affecting the Banyupahit waters by using stable isotope, chemical and mineralogical data collected from sites along the stream length. The saturation of the stream waters with respect to minerals was evaluated with SOLVEQ and WATEQ4F and compared with the geochemical observations. An aluminous mineralogy (alunogen, pickeringite, tamarugite and kalinite) develops in the upper part of the Banyupahit due to concentration of the headwaters by evaporation. Downstream attenuation of dissolved element concentrations results principally from dilution and from mineral precipitation. The stream pH changes from 0 at the source to >4 close to the mouth. The δD and δ¹⁸O values and the relative SO₄–Cl–F contents of the Banyupahit waters indicate that the tributaries are mostly meteoric. Dissolved SO₄ in the acidic stream come only from the crater lake seepages and are not involved later in microbially mediated reactions, as shown by their δ³⁴S and δ¹⁸O values. Re-equilibration of the stream SO₄ oxygen-isotope composition with H₂O from tributaries does not occur.Calcium, SiO₂, Al, Fe, K and SO₄ behave non-conservatively in the stream waters. Gypsum, silica (amorphous or poorly ordered), a basic aluminum hydroxysulfate (basaluminite?), K-jarosite and amorphous ferric hydroxide may exert a solubility control on these elements along the entire stream length, or in certain stream sections, consistent with the thermochemical model results. Downstream concentration trends and mineral saturation levels suggest that precipitation of Sr-, Pb-rich barite and celestite consume Ba, Sr and Pb, whereas dissolved Cu, Pb and Zn may adsorb onto solid particles, especially after the junctions of the acidic stream with non-acidic rivers. We calculated that significant fluxes of SO₄, F, Cl, Al, SiO₂, Ti, Mn and Cu may reach the irrigation system, possibly causing serious environmental impacts such as soil acidification and induration.     

Addition of magmatic volatiles into the hot spring waters of loowit canyon,Mount St. Helens,Washington, USA

Geochemical studies on cold meteoric waters, post-1980 hot spring waters, fumarole emissions from the dacite dome, and volcanic rocks at Mount St. Helens (MSH) from 1985 to 1989 show that magmatic volatiles are involved in the formation of a new hydrothermal system. Hot spring waters are enriched in ¹⁸O by as much as 2 and display enrichments in D relative to cold waters. A well-defined isotopic trend is displayed by the isotopic composition of a>400°C fumarole condensate collected from the central crater in 1980 (-33 D, +6 ¹⁸O), of condensate samples collected on the dome, and of cold meteoric and hot spring waters. The trend indicates that mixing occurs between local meteoric water and magmatic water degassing from the dacite dome. Between 30 and 70% magmatic water is present in the dome fumarole discharges and 10% magnatic water has been added to the waters of the hydrothermal system. Relations between Cl, SO₄ and HCO₃ indicate that the hot spring waters are immature volcanic waters formed by reaction of rocks with waters generated by absorption of acidic volcanic fluids. In addition, the B/Cl ratios of the spring waters are similar to the B/Cl ratios of the fumarole condensates (0.02), values of ¹³C in the HCO₃ of the hot springs (-9.5 to-13.5) are similar to the magmatic value at MSH (-10.5), and the ³He/⁴He ratio, relative to air, in a hot spring water is 5.7, suggesting a magmatic origin for this component.managed by Martin Marietta Energy Systems, Inc., under contract DE-AC05-84OR21400 with the US Department of Energy     

Isotopic variation in the lake water balance at the Yamdruk‐tso basin,southern Tibetan Plateau

The use of stable isotopes is a practical tool in the study of the lake water budget. This is an one way to study the hydrological cycle in the large numbers of inland lakes on the Tibetan Plateau, in which the isotope record of the sediment is believed to reflect the climatic and environmental changes. The monitoring of stable isotopes of the precipitation, river and lake waters during 2004 in the inland Yamdruk‐tso basin, southern Tibetan Plateau, reveals the lake water δ¹⁸O is over 10‰ higher than the local precipitation. This high difference indicates strong isotope enrichment due to lake water evaporation. The simulation results based on the isotope technique show that the present lake water δ¹⁸O level corresponds to an average relative humidity of around 54–58% during evaporation, which is very close to the instrumental observation. The simulation results also show that the inland lakes on the Tibetan Plateau have a strong adjustability to the isotope shift of input water δ¹⁸O. On average, the isotope component in the inland lake water is to a large extent controlled by the local relative humidity, and can also be impacted by a shift of the local precipitation isotope component. This is probably responsible for the large consistence in the isotope component in the extensive inland lakes on the Tibetan Plateau. Copyright © 2008 John Wiley & Sons, Ltd.     

Trace metals and radium in the Gulf of Mexico: An evaluation of river and continental shelf sources

Several studies have provided evidence for the enrichment of trace elements in coastal waters, particularly for copper. These enrichments have been attributed to diffusion from continental shelf sediments and to an influx of river water. We attempted to resolve between these sources by undertaking an extensive suite of measurements of trace metals (Cu, Ni, Cd), ²²⁶Ra and ²²⁸Ra in the surface waters of the Gulf of Mexico, along with trace metal profiles at 6 stations (April 1981 and December 1982). These data establish that enrichments of copper, nickel and cadmium occur in the shallow waters of the Gulf of Mexico. On the Mississippi continental shelf, high trace element concentrations (Cu, Ni: ～ 9 nmol/kg; Cd: ～ 200 pmol/kg) in lower-salinity waters (26‰) are similar to those observed in the Mississippi plume at the same salinity. This evidence suggests a river water source. On the other hand, trace element enrichments are also observed in the northern Gulf (Cu: +0.4 nmol/kg; Ni: +0.5 nmol/kg; Cd: +20 pmol/kg) which coincide with an increase in ²²⁸Ra but are not accompanied by decreased salinity. The excess of evaporation over precipitation in this region makes it possible that this water could be evaporated estuarine water; therefore, hydrographic observations cannot distinguish readily between river and shelf sources. A regional flux balance shows that most of the excess copper in the surface waters of the Florida Current can be supplied by the river-borne dissolved copper flux. Within the uncertainties of such calculations, the continental shelf copper flux must be less than or equal to the river flux.     

Groundwater dating with 3H and SF6 in relation to mixing patterns,transport modelling and hydrochemistry

A comprehensive study of a sandy aquifer of deltaic origin in southern Poland included water chemistry, isotopes, dissolved trace gases and transport modelling. Tritium, sulphur hexafluoride (SF₆) and freons (F‐11, F‐12 and F‐113) showed the presence of modern waters in the recharge areas and shallow confined parts of the aquifer. The presence of older Holocene waters farther from the recharge areas was indicated by lack of ³H, SF₆ contents ≤0·02 fmol l⁻¹ and relatively low ¹⁴C values. The discharge from the system is by upward seepage in the valley of a major river. Pre‐Holocene waters of a cooler climate, identified on the basis of δ¹⁸O, δ²H, ¹⁴C, Ne and Ar data, were found in some distant wells. Concentrations of N₂, Ne and Ar determined by gas chromatography were used for calculating the noble gas temperatures, air excess needed for correction of SF₆, and nitrogen content released by denitrification process. The time series of ³H content available for some wells supplied quantitative information on age distributions and the total mean ages of flow through the unsaturated and saturated zones. The derived ³H age distributions turned out to be very wide, with mean values in the range of about 30 to 160 years. For each well with determined ³H age, the SF₆ data showed either a lower age range or the possibility of a lower age as expected due to shorter travel times of SF₆ through the unsaturated zone, which most probably also resulted in different types of age distributions of these tracers. Freons appeared to be of little use for individual age determinations. A quantitative estimation of two‐component mixing from SF₆ ³H relations is not possible unless the travel time of ³H through the unsaturated zone is comparable to that of SF₆. The ratio of integrals of the response function over the age range with tracer and the whole response function yields the ratio of water with tracer to total flow of water. That ratio is a tracer‐dependent function of time. Transport modelling of SF₆ tracer done with MT3D code yielded initially large discrepancies between calculated and measured tracer concentrations. Some discrepancies remained even after calibration of the transport model with SF₆. Simulation of tritium contents with a calibrated transport model yielded reasonable agreement with measured contents in some wells and indicated a need for further investigations, particularly in the eastern part of the aquifer. The existence of distinct hydrochemical zones is consistent with the tracer data; young waters with measurable ³H and SF₆ contents are aerobic and of HCO₃ Ca or HCO₃ SO₄ Ca types. Slightly elevated Na and Cl contents, as well as the highest concentrations of SO₄ and NO₃ within this zone are due to anthropogenic influences. Anaerobic conditions prevail in the far field, under the confining cover, where pre‐bomb era Holocene waters dominate. In that zone, dissolved oxygen, NO₃ and U contents are reduced, and Fe, Mn and NH₄ contents increase. In the third zone, early Holocene and glacial waters occur. They are of HCO₃ Ca Na or HCO₃ Na types, with TDS values higher than 1 g l⁻¹ and Na content higher than 200 mg l⁻¹, due to either small admixtures of ascending or diffusing older water or freshening of marine sediments, a process that is probably occurring till the present time. Copyright © 2005 John Wiley & Sons, Ltd.     

Geological evolution of a pleistocene rhyolitic center — Sierra La Primavera, Jalisco, México

The Sierra La Primavera volcanic complex consists of late Pleistocene comenditic lava flows and domes. ash-flow tuff, air-fall pumice, and cold caldera-lake sediments. The earliest lavas were erupted about 120,000 years ago, and were followed approximately 95,000 years ago by the eruption of about 20 km³ of magma as ash flows that form the compositionally-zoned Tala Tuff. Collapse of the roof zone of the magma chamber led to the formation of a shallow 11-km-diameter caldera. It soon filled with water, forming a caldera lake in which sediment began to collect. At about the same time, two central domes erupted through the middle of the lake and a “giant pumice horizon”, an important stratigraphic marker, was deposited. Shortly thereafter ring domes erupted along two parallel arcs: one along the northeast portion of the ring fracture, and the other crossing the middle of the lake. All these events occurred during a period of approximately 5,000–10,000 years. Sedimentation continued and a period of volcanic quiescence was marked by the deposition of some 30 m of fine-grained ashy sediments virtually free from pumice lapilli. Approximately 75,000 years ago, a new group of ring domes erupted at the southern margin of the lake. These domes are lapped by only 10–20 m of sediments, as uplift resulting from renewed insurgence of magma brought an end to the lake. This uplift culminated in the eruption, beginning approximately 60,000 years ago, of aphyric lavas along a southern arc. The youngest of these lavas erupted approximately 20,000–30,000 years ago.The four major fault systems in the Sierra La Primavera are related to caldera collapse or to uplift caused by the insurgence of the southern are magma. Steam vents and larga-discharge 65°C hot springs are associated with the faulting. Calculated equilibrium temperatures of the geothermal fluids are 170°C, but temperatures in excess of 240°C have been encountered in an exploratory drill hole.A seismic survey showed attenuation of both S and P waves within the caldera, P waves attenuated more severely than S waves. The greatest attenuation is associated with an area of steam vents, and the rapid lateral variations in attenuation suggest that they are produced by a shallow geothermal system rather than by underlying magma.