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

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

Geochemistry 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.     

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.     

Gravity and magnetic signatures of volcanic plugs related to Deccan volcanism in Saurashtra, India and their physical and geochemical properties

The Bouguer anomaly and the total intensity magnetic maps of Saurashtra have delineated six circular gravity highs and magnetic anomalies of 40-60 mGal (10⁻⁵m/s²) and 800-1000 nT, respectively. Three of them in western Saurashtra coincide with known volcanic plugs associated with Deccan Volcanic Province (DVP), while the other three in SE Saurashtra coincide with rather concealed plugs exposed partially. The DVP represents different phases of eruption during 65.5±2.5 Ma from the Reunion plume. The geochemical data of the exposed rock samples from these plugs exhibit a wide variation in source composition, which varies from ultramafic/mafic to felsic composition of volcanic plugs in western Saurashtra and an alkaline composition for those in SE Saurashtra. Detailed studies of granophyres and alkaline rocks from these volcanic plugs reveal a calc-alkaline differentiation trend and a continental tectonic setting of emplacement. The alkaline plugs of SE Saurashtra are associated with NE-SW oriented structural trends, related to the Gulf of Cambay and the Cambay rift basin along the track of the Reunion plume. This indicates a deeper source for these plugs compared to those in the western part and may represent the primary source magma. The Junagadh plug with well differentiated ring complexes in western Saurashtra shows well defined centers of magnetic anomaly while the magnetic anomalies due to other plugs are diffused though of the same amplitude. This implies that other plugs are also associated with mafic/ultramafic components, which may not be differentiated and may be present at subsurface levels. Paleomagnetic measurements on surface rock samples from DVP in Saurashtra suggest a susceptibility of 5.5×10⁻² SI units with an average Koenigsberger ratio (Q_n) of almost one and average direction of remanent magnetization of D=147.4° and I=+56.1°. The virtual geomagnetic pole (VGP) position computed from the mean direction of magnetization for the volcanic plugs and Deccan basalt of Saurashtra is 30°N and 74°W, which is close to the VGP position corresponding to the early phases of Deccan eruption. Modeling of gravity and magnetic anomalies along two representative profiles across Junagadh and Barda volcanic plugs suggest a bulk density of 2900 and 2880 kg/m³, respectively and susceptibility of 3.14×10⁻² SI units with a Q_n ratio of 0.56 which are within the range of their values obtained from laboratory measurements on exposed rock samples. The same order of gravity and magnetic anomalies observed over the volcanic plugs of Saurashtra indicates almost similar bulk physical properties for them. The inferred directions of magnetization from magnetic anomalies, however, are D=337° and 340° and I=−38° and −50° which represent the bulk direction of magnetization and also indicate a reversal of the magnetic field during the eruption of these plugs. Some of these plugs are associated with seismic activities of magnitude ≤4 at their contacts. Based on this analysis, other circular/semi-circular gravity highs of NW India can be qualitatively attributed to similar subsurface volcanic plugs.     

A Hybrid Model for the Summit Region of Merapi Volcano,Java, Indonesia,Derived from Gravity Changes and Deformation Measured between 2000 and 2002

Three-dimensional displacements and gravity changes were measured at 20 points between 2000 and 2002 at Merapi volcano, Java, Indonesia. Former models focused on the modeling of a single magmatic source located in the summit region of the volcano. Such models do not fit to our measurements between 2000 and 2002. A new hybrid model approach is developed consisting of an elastic-gravitational source described by a mass and energy term as well as a combined dip-slip/strike-slip fault zone in the summit region. Both nonlinear optimization problems, given by the common inversion of three-dimensional displacements and gravity changes, are solved by applying a genetic algorithm. The hybrid model fits the measurements accurately, tested by Fisher test statistics. Furthermore, our model for Merapi volcano confirms previous structural models for this region so that the new model is statistically proven as well as physically reliable.     

Leakage of Active Crater lake brine through the north flank at Rincón de la Vieja volcano, northwest Costa Rica, and implications for crater collapse

The Active Crater at Rincón de la Vieja volcano, Costa Rica, reaches an elevation of 1750 m and contains a warm, hyper-acidic crater lake that probably formed soon after the eruption of the Rio Blanco tephra deposit approximately 3500 years before present. The Active Crater is buttressed by volcanic ridges and older craters on all sides except the north, which dips steeply toward the Caribbean coastal plains. Acidic, above-ambient-temperature streams are found along the Active Crater's north flank at elevations between 800 and 1000 m. A geochemical survey of thermal and non-thermal waters at Rincón de la Vieja was done in 1989 to determine whether hyper-acidic fluids are leaking from the Active Crater through the north flank, affecting the composition of north-flank streams.Results of the water-chemistry survey reveal that three distinct thermal waters are found on the flanks of Rincón de la Vieja volcano: acid chloride–sulfate (ACS), acid sulfate (AS), and neutral chloride (NC) waters. The most extreme ACS water was collected from the crater lake that fills the Active Crater. Chemical analyses of the lake water reveal a hyper-acidic (pH0) chloride–sulfate brine with elevated concentrations of calcium, magnesium, aluminum, iron, manganese, copper, zinc, fluorine, and boron. The composition of the brine reflects the combined effects of magmatic degassing from a shallow magma body beneath the Active Crater, dissolution of andesitic volcanic rock, and evaporative concentration of dissolved constituents at above-ambient temperatures. Similar cation and anion enrichments are found in the above-ambient-temperature streams draining the north flank of the Active Crater. The pH of north-flank thermal waters range from 3.6 to 4.1 and chloride:sulfate ratios (1.2–1.4) that are a factor of two greater than that of the lake brine (0.60). The waters have an ACS composition that is quite different from the AS and NC thermal waters that occur along the southern flank of Rincón de la Vieja.The distribution of thermal water types at Rincón de la Vieja strongly indicates that formation of the north-flank ACS waters is not due to mixing of shallow, steam-heated AS water with deep-seated NC water. More likely, hyper-acidic brines formed in the Active Crater area are migrating through permeable zones in the volcanic strata that make up the Active Crater's north flank. Dissolution and shallow subsurface alteration of north-flank volcanoclastic material by interaction with acidic lake brine, particularly in the more permeable tephra units, could weaken the already oversteepened north flank of the Active Crater. Sector collapse of the Active Crater, with or without a volcanic eruption, represents a potential threat to human lives, property, and ecosystems at Rincón de la Vieja volcano.     

Origin, characteristics, and behaviour of lahars following the 1990 eruption of Kelud volcano, eastern Java (Indonesia)

 In contrast to most twentieth-century eruptions of Kelud volcano (eastern Java), the 10 February 1990 plinian eruption was not accompanied by lake-outburst lahars. However, at least 33 post-eruption lahars occurred between 15 February and 28 March 1990. They swept down 11 drainage systems and travelled as far as 24 km at an estimated mean peak velocity in the range of 4–11 m s^–1. The deposits (volume ≥30 000 000 m³) were approximately 7 m thick 2 km from vent, and 3 m thick 10 km from vent, on the volcaniclastic apron surrounding the volcano. Subtle but significant sedimentological differences in the deposits relate to four flow types: (a) Early, massive deposits are coarse, poorly sorted, slightly cohesive, and commonly inversely graded. They are inferred to record hot lahars that incorporated pumice and scoria from pyroclastic-flow deposits, probably by rapid remobilization of hot proximal pyroclastic flow deposits by rainfall runoff. Sedimentary features, such as clasts subparallel to bedding and thick, reversely to ungraded beds, suggest that these flows were laminar. (b) Abundant, very poorly sorted deposits include non-cohesive, clast-supported, inversely graded beds and ungraded, finer-grained, and cohesive matrix-supported beds. These beds display layering and vertical segregation/density stratification, suggesting unsteady properties of pulsing debris flows. They are interpreted as deposited from segments of flow waves at a middle distance downstream that incorporated pre-eruption sediments. Sedimentological evidence suggests unsteady flow properties during progressive aggradation. (c) Fine-grained, poorly sorted and ungraded deposits are interpreted as recording late hyperconcentrated streamflows that formed in the waning stage of an overflow and transformed downcurrent into streamflows. (d) Ungraded, crudely stratified deposits were emplaced by flows transitional between hyperconcentrated flows and streamflows that traveled farther downvalley (as far as 27 km from the vent). At Kelud, the transformation of flow and behavior occurs within only 10 km of the source, at the apex of the alluvial fans. The rapid change of flow behavior is attributed to the low fines content and to the unsteady flow regime, which may be due to: (a) the rapid deposition of bedload, owing to the break in channel gradient close to the vent and to changes in channel cross-section and roughness; and (b) the very low silt+clay content in the non-cohesive deposits. These deposits mix with water to produce streamflows. Received: 27 June 1997 / Accepted: 5 January 1998     

Occurrence and chemical composition of the Eoarchean carbonate rocks of the Nulliak supracrustal rocks in the Saglek Block of northeastern Labrador,Canada

The Eoarchean Nulliak supracrustal rocks in the Saglek Block of northeastern Labrador, Canada, contain some of the world's oldest carbonate rocks. This work attempted to reveal the origin of the carbonate rocks and estimate the surface environmental conditions of the early Earth based on their occurrence and geochemistry. They occur together with mafic and ultramafic rocks in Pangertok Inlet and St. John's Harbour South, whereas they are interlayered with pelitic rock layers with quartzofeldspathic mineral assemblages in St. John's Harbour East and Big Island. The geological occurrence suggests that the formers were formed around hydrothermal fields, whereas the latters were deposited near a continental margin. Some carbonate rocks have high SiO₂, Al₂O₃, and Zr contents, indicating that the silicification and involvement of detrital materials influenced their composition; thus, pure carbonate rocks were selected using a combined filter of the SiO₂, TiO_2, Al₂O₃, Zr, and Ba contents. The selected carbonate rocks have positive La, Eu, Gd, Y, U, Pb, and Sr anomalies, negative Nb, Zr, and Hf anomalies, and relatively small enrichment in heavy rare earth elements (HREEs). The La and Y anomalies suggest that they originated from chemical sediments precipitated from seawater. On the other hand, the small HREE-enrichment suggests that REEs were mainly dissolved as REE-carbonate complexes in seawater or that the riverine influxes were dominated by the detritus of Eoarchean continental crusts, presumably composed of HREE-depleted TTG. The U anomaly suggests that uranium was more dissolved than Th as U-bearing carbonate complexes in seawater. The Nulliak carbonate rocks also show a positive correlation between Y and Eu anomaly values, suggesting that the precipitation of iron-oxyhydroxide causing the Y anomaly was more significant near the hydrothermal fields than the continental margin, consistent with an alkaline hydrothermal model.