Shock-induced volatile loss from a carbonaceous chondrite: implications for planetary accretion

Solid-recovery impact-induced volatile loss experiments on the Murchison C2M meteorite indicate that for an impact of a given velocity, H₂O and total volatiles are driven from the sample in the same proportion as present initially. We infer that the volatiles other than H₂O driven from the meteorite also have the same bulk composition as those of the starting material. Thus, the early bulk composition of an impact-induced atmosphere of a planet growing by accretion from material like Murchison would be the same as the volatile composition of the incident planetesimals. Incipient devolatilization of Murchison occurs at an initial shock pressure of about 11 GPa and complete devolatilization occurs at a pressure of about 30 GPa. If an Earth-sized planet were formed from the infall of planetesimals of Murchison composition, incipient and complete devolatilization of accreting planetesimals would occur when the planet reached approximately 12% and 27%, respectively, of its final radius. Thus, impact-induced devolatilization of accreting planetesimals and of the hydrated surface would profoundly affect the distribution of volatiles within the accreting planet. For example, for a cold, homogeneous accretion of a planet, prior to metallic core formation and internal differentiation, the growing planet would have a very small core with the same volatile content as the incident material, a volatile-depleted “mantle”, and an extremely volatile-rich surface.     

Molecular and carbon isotopic compositions of gas inclusions of deep carbonate rocks in the Tarim Basin

Gaseous components of gas inclusions in deep carbonate rocks (>5700 m) from the Tacan 1 well were analyzed by online mass spectrometry by means of either the stepwise heating technique or vacuum electromagnetism crushing. The carbon isotopic compositions of gases released by vacuum electromagnetism crushing were also measured. Although the molecular compositions of gas inclusions show differences between the two methods, the overall characteristics are that gas inclusions mainly contain CO2, whilst hydrocarbon gases, such as CH4, C2H6 and C3H8, are less abundant. The content of CO is higher in the stepwise heating experiment than that in the method of vacuum electromagnetism crushing, and there are only minor amounts of N2, H2 and O2 in gas inclusions. Methane δ13C values of gas inclusions in Lower Ordovician and Upper Cambrian rocks (from 5713.7 to 6422 m; -52‰-63‰) are similar to those of bacterial methane, but their chemical compositions do not exhibit the dry character in comparison with biogenic gases. These characteristics of deep gas inclusions may be related to the migration fractionation. Some deep natural gases with light carbon isotopic characteristics in the Tazhong Uplift may have a similar origin. The δ13C1 values of gas inclusions in Lower Cambrian rocks (7117-7124 m) are heavier (-39‰), consistent with highly mature natural gases. Carbon isotopic compositions of CO2 in the gas inclusions of deep carbonate rocks are similar (from -4‰ to -13‰) to those of deep natural gases, indicating predominantly an inorganic origin.     

FeO and H2O and the homogeneous accretion of the earth

We present new shock devolatilization recovery data for brucite (Mg(OH)₂) shocked to 13 and 23 GPa. These data combined with previous data for serpentine (Mg₃Si₂O₅(OH)₄) are used to constrain the minimum size terrestrial planet for which planetesimal infall will result in an impact-generated water atmosphere. Assuming a chondritic abundance of minerals including 3–6%, by mass water, in hydrous phyllosilicates, we carried out model calculations simulating the interaction of metallic iron with impact-released free water on the surface of the accreting Earth. We assume that the reaction of water with iron in the presence of enstatite is the prime source of the terrestrial FeO component of silicates and oxides. Lower and upper bounds on the terrestrial FeO budget are based on mantle FeO content and possible incorporation of FeO in the outer core. We demonstrate that the iron-water reaction would result in the absence of atmospheric/hydrospheric water, if homogeneous accretion is assumed. In order to obtain10²⁵g of atmospheric water by the end of accretion, slightly heterogeneous accretion with initially 36% by mass iron planetesimals, as compared to a homogeneous value of 34% is required. Such models yield final FeO budgets, which either require a higher FeO content of the mantle (17 wt.%) or oxygen as a light element in the outer core of the Earth.     

Hydrogen isotope composition of natural gases from the Tarim Basin and its indication of depositional environments of the source rocks

By measuring carbon and hydrogen isotope compositions for C1, C2 and C3 of 74 gas samples, natural gases from the Tarim Basin can be divided into six groups on the basis of their origins: (1) coal-type gas derived from coal measures; (2) coal-type gas generated from the T-J lacustrine mudstones; (3) oil-type gas derived from the Cambrian and low Ordovician marine source rocks; (4) oil-type gas from the source rocks deposited in the marine-transitional facies; (5) mixing gas between gas derived from the Carboniferous transitional source rocks and the Mesozoic humic gas, and (6) mixing gases of thermal genetic gas and little deep gas in the Southwest depression of the Tarim Basin. The δ D values of methane in natural gases originating from different type kerogens are affected by both palaeo-environments of the source rock formation (kerogen types) and thermal maturity, with sedimentary environment (kerogen type) as the main controlling factor. Under the similar thermal maturity, the hydrogen isotope composition of methane is more enriched in deuterium in marine environments than lacustrine one. With the increase of thermal maturity and the increase of carbon atomic numbers of gaseous alkanes, the hydrogen isotopes become enriched in deuterium. The δ D values of ethane and propane (δ D2, δ D3) are controlled mainly by thermal maturity and to a lesser degree by sedimentary environment of the source rock formation. The partial reversal of hydrogen isotopes for gaseous alkanes would be related to the microbial oxidation, mixing of sapropelic and humic gases and / or mixing of gases from similar kerogen sources with various thermal maturities. In the oil-type gas, the sulfate reduction reaction would result in the reversed order of δ D1 and δ D2 (e.g. δ D1>δ D2).     

Carbon isotopic fractionation in the process of Fischer-Tropsch reaction in primitive solar nebula

Carbon isotopic fractionation of low-weight molecules of the products of Fischer-Tropsch reaction under the conditions of Earth's accumulation region in primitive solar nebula has been experimentally studied. Among the reaction products, carbon dioxide has the heaviest isotopic composition; carbon isotopic composition of methane has a large variation; different from biogenic natural gases, carbon isotopic compositions among ethane, propane and butane yield a reverse distribution pattern. It suggests that primordial hydrocarbons that were captured in the interior of the Earth during its accretion possess a reverse carbon isotopic distribution pattern. Project supported by the National Natural Science Foundation of China (Grant No. 49233060).     

Accretion, core formation, H and C evolution of the Earth and Mars

Recent understandings of planetary accretion have suggested that accumulation of a small number of large planetesimals dominates intermediate to final growth stages of the terrestrial planets, with impact velocity high enough to induce extensive melting of the planetesimal and target materials, resulting in formation of a large molten region in which gravitational segregation of silicate and metal, that is, core formation proceeds. In case of homogeneous accretion, volatiles contained in each planetesimal are likely subjected to partitioning among gas, silicate melt, and molten metallic iron at significantly high temperatures and pressures in such a massive molten region. Each phase would subsequently form the proto-atmosphere, -mantle, or-core, respectively. Such chemical reprocessing of H and C associated with core formation, which is followed by both degassing from mantle and atmospheric escape, may result in a diverse range of H₂O/CO₂ in planetary surface environments, which mainly depends on the H and C content relative to metallic iron in planetary building stones. This may explain inferred difference in volatile distribution between the Earth's (relatively H₂O-rich, CO₂-poor) and the martian (H₂O-poor, CO₂-rich) surface environments. Such volatile redistribution may be systematically described by using the retentivity of H₂O, ξ, defined as follows: ξ = 1 − ([CO]⁰ + 2[CH₄]⁰ + 2[C(gr)]⁰)/[H₂O]⁰, where [i]⁰ represents mol number of species i partitioned into non-metallic phases, that is, gas and silicate melt in impact-induced molten region. When ξ > 0.5, relatively H₂O-rich and CO₂-poor surface environment may eventually evolve, although a small portion of H₂O partitioned into the NON=metallic phases are possibly consumed by subsequent chemical reactions with reduced C-species with producing CO₂ and H₂. When ξ< 0.5, on the contrary, H₂O consumption by the above reactions and selective loss of H₂ to space may result in relative H₂O-depleted and CO₂-rich surface environment. Given the building stone composition by the two-component model by Ringwood (1977) and Wänke (1981), ξ is found to decrease with increasing the mixing fraction of the volatile-rich component: ξ > 0.5 for the mixing fraction smaller than about 15–20% and ξ < 0 for the mixing fraction larger than about 20–30%. This is not significantly dependent on temperature and pressure in molten region and H/C ratio in the building stone. The estimated mixing fraction of the volatile-rich component, about 10% for the Earth and 35% for Mars, is consistent with the observed difference in volatile distribution between the surfaces of both planets.     

Shock-induced devolatilization of calcite

The amounts of CO₂ and CO evolved upon shock compression and decompression of calcite to 18 GPa (180 kbar) have been determined using a new gas phase shock recovery technique and gas source mass spectrometry. The data demonstrate that from ～0.03 to 0.3 mole percent of calcite is devolatilized at shock pressures significantly lower than those predicted (30 GPa) for the onset of volatilization by continuum thermodynamic theory and are in qualitative agreement with release adiabat data for calcite and aragonite. Carbon and oxygen isotope ratios in the shock-released CO₂ are the same as those in the unshocked (hydrothermal) calcite, demonstrating that the CO₂ comes from the calcite rather than other potential sources.     

Primary migration and secondary alteration of the Upper Paleozoic gas reservoir in Ordos Basin,China―Application of fluid inclusion gases

The composition of fluid inclusions(FI)often represents the initial geochemical characteristics of palaeo-fluid in reservoir rock.Influence on composition and carbon isotopic composition of gas during primary migration,reservoir-forming and subsequent secondary alterations are discussed through comparing fluid inclusion gas with coal-formed gas and natural gas in present gas reservoirs in the Ordos Basin.The results show that primary migration of gas has significant effect on the molecular but not on the carbon isotopic composition of methane.Migration and diffusion fractionation took place during the secondary migration of gas in Upper Paleozoic gas reservoir according to carbon isotopic composition of methane in FIs.Composition and carbon isotopic composition of natural gas were nearly unchanged after the gas reservoir forming through comparing the FI gases with the natural gas in present gas reservoir.     

Primary migration and secondary alteration of the Upper Paleozoic gas reservoir in Ordos Basin,China — Application of fluid inclusion gases

The composition of fluid inclusions (FI) often represents the initial geochemical characteristics of palaeo-fluid in reservoir rock. Influence on composition and carbon isotopic composition of gas during primary migration, reservoir-forming and subsequent secondary alterations are discussed through comparing fluid inclusion gas with coal-formed gas and natural gas in present gas reservoirs in the Ordos Basin. The results show that primary migration of gas has significant effect on the molecular but not on the carbon isotopic composition of methane. Migration and diffusion fractionation took place during the secondary migration of gas in Upper Paleozoic gas reservoir according to carbon isotopic composition of methane in Fls. Composition and carbon isotopic composition of natural gas were nearly unchanged after the gas reservoir forming through comparing the FI gases with the natural gas in present gas reservoir.     

Rare gas isotopes and mass fractionation: An indicator of gas transport into or from a magma

A simple model of mass fractionation may explain the isotopic ratios of rare gases in volcanic materials. Single-stage mass fractionation of atmospheric rare gases predicts an upper limit for²⁰Ne/²²Ne of 10.3 and a lower limit for⁴⁰Ar/³⁶Ar of 280. The rare gas data in volcanic materials seem to support this interpretation.Relatively low⁴⁰Ar/³⁶Ar ratios, as low as 282, have been observed in recent Japanese volcanic rocks. Such a low⁴⁰Ar/³⁶Ar ratio may be explained by mass fractionation of the atmospheric value if the rare gases represent those which were transported into the magma chamber with other volatile elements.Both the amounts and the fractionated rare gas abundance pattern of lighter elements which are observed in pumices from the recent eruption of Mt. Usu, Southern Hokkaido, Japan, suggest the possibility of air injection into its magma chamber. Thus, the fractionation of rare gases in volcanic materials may be a common occurrence, and it must be considered in models for the origin of isotopic differences between rare gases in volcanic materials and the atmosphere.     

Kinetic model of ammonia synthesis in the solar nebula

The synthesis of ammonia in the primitive solar nebula was probably catalyzed by metallic iron grains because the gas phase reaction is kinetically inhibited. A preliminary kinetic model predicts a maximum of 3% of the nitrogen in the form of ammonia at the time of planetary accretion. Rates of reaction were derived from industrial data on ammonia iron catalysts. Due to the low rates of reaction, molecular nitrogen remains the dominant species even at the low temperatures where chemical equilibrium favors ammonia formation. Thus planetary atmospheres formed from a reservoir composed largely of molecular nitrogen. The non-equilibrium volatile gases (CO and N₂) suggested to comprise most of the carbon and nitrogen in comets is consistent with the model.     

Primary migration and secondary alteration of the Upper Paleozoic gas reservoir in Ordos Basin,China — Application of fluid inclusion gases

The composition of fluid inclusions (FI) often represents the initial geochemical characteristics of palaeo-fluid in reservoir rock. Influence on composition and carbon isotopic composition of gas during primary migration, reservoir-forming and subsequent secondary alterations are discussed through comparing fluid inclusion gas with coal-formed gas and natural gas in present gas reservoirs in the Ordos Basin. The results show that primary migration of gas has significant effect on the molecular but not on the carbon isotopic composition of methane. Migration and diffusion fractionation took place during the secondary migration of gas in Upper Paleozoic gas reservoir according to carbon isotopic composition of methane in Fls. Composition and carbon isotopic composition of natural gas were nearly unchanged after the gas reservoir forming through comparing the FI gases with the natural gas in present gas reservoir.

     

D/H ratios in speleothem fluid inclusions: A guide to variations in the isotopic composition of meteoric precipitation?

D/H ratios of fluid inclusion waters extracted from²³⁰Th/²³⁴U-dated speleothems that were originally deposited under conditions of isotopic equilibrium should provide a direct estimate of the hydrogen isotopic composition of ancient meteoric waters. We present here D/H ratios for 47 fluid inclusion samples from thirteen speleothems deposited over the past 250,000 years at cave sites in Iowa, West Virginia, Kentucky and Missouri. At each site glacial-age waters are depleted in deuterium relative to those of interglacial age. The average interglacial/glacial shift in the hydrogen isotopic composition of meteoric precipitation over ice-free areas of east-central North America is estimated to be ?12‰. This shift is consistent with the present climatic models and can be explained in terms of the prevailing pattern of atmospheric circulation and an increased ocean-continent temperature gradient during glacial times which more than compensated for the increase in deuterium content of the world ocean.     

Gas and hydrogen isotopic analyses of volcanic eruption clouds in Guatemala sampled by aircraft

Gas samples were collected by aircraft entering volcanic eruption clouds of three Guatemalan volcanoes. Gas chromatographic analyses show higher H₂ and S gas contents in ash eruption clouds and lower H₂ and S gases in vaporous gas plumes. H isotopic data demonstrate lighter isotopic distribution of water vapor in ash eruption clouds than in vaporous gas plumes. Most of the H₂O in the vaporous plumes is probably meteoric. The data are the first direct gas analyses of explosive eruptive clouds, and demonstrate that, in spite of atmospheric admixture, useful compositional information on eruptive gases can be obtained using aircraft.     

Mineralogy and hydrogen isotope geochemistry of clay minerals in the Ohnuma geothermal area,Northeastern Japan

Mineralogical and hydrogen isotopic studies have been made on clay minerals occurring in the Ohnuma geothermal area, northeastern Japan. Here, clay minerals such as smectite, kaolinite, dickite, sericite, and chlorite were formed by hydrothermal alteration of Miocene rocks. A chemical equilibrium can be assumed to be attained from the fact that the amount of expandable layer in the interstratified chlorite/smectite decreases and the polytype of sericite changes from 1M to 2M₁ with increasing depth and temperature. The hydrogen isotopic composition (D/H) of the clay minerals is lighter than that of the geothermal and local meteoric waters by about 20–40‰. The hydrogen isotopic fractionation factors α_{mineral-water} are as follows: 0.972–0.985 for kaolinite and dickite, 0.973–0.977 for sericite, and 0.954–0.987 for chlorite. In the temperature range from 100 to 250°C, the hydrogen isotopic fractionation factors between these minerals and water are not sensitive to the temperature. α_{chlorite-water} depends on the kind of octahedrally coordinated cations which lie close to the hydroxyl groups; it becomes large with an increase of Mg content of chlorite.     

The origins and concentrations of water,carbon, nitrogen and noble gases on Earth

The isotopic compositions of terrestrial hydrogen and nitrogen are clearly different from those of the nebular gas from which the solar system formed, and also differ from most of cometary values. Terrestrial N and H isotopic compositions are in the range of values characterizing primitive meteorites, which suggests that water, nitrogen, and other volatile elements on Earth originated from a cosmochemical reservoir that also sourced the parent bodies of primitive meteorites. Remnants of the proto-solar nebula (PSN) are still present in the mantle, presumably signing the sequestration of PSN gas at an early stage of planetary growth. The contribution of cometary volatiles appears limited to a few percents at most of the total volatile inventory of the Earth. The isotope signatures of H, N, Ne and Ar can be explained by mixing between two end-members of solar and chondritic compositions, respectively, and do not require isotopic fractionation during hydrodynamic escape of an early atmosphere.The terrestrial inventory of ⁴⁰Ar (produced by the decay of ⁴⁰K throughout the Earth's history) suggests that a significant fraction of radiogenic argon may be still trapped in the silicate Earth. By normalizing other volatile element abundances to this isotope, it is proposed that the Earth is not as volatile-poor as previously thought. Our planet may indeed contain up to ~ 3000 ppm water (preferred range: 1000–3000 ppm), and up to ~ 500 ppm C, both largely sequestrated in the solid Earth. This volatile content is equivalent to an ~ 2 (± 1) % contribution of carbonaceous chondrite (CI-CM) material to a dry proto-Earth, which is higher than the contribution of chondritic material advocated to account for the platinum group element budget of the mantle. Such a (relatively) high contribution of volatile-rich matter is consistent with the accretion of a few wet planetesimals during Earth accretion, as proposed by recent dynamical models.The abundance pattern of major volatile elements and of noble gases is also chondritic, with two notable exceptions. Nitrogen is depleted by one order of magnitude relative to water, carbon and most noble gases, which is consistent with either N retention in a mantle phase during magma generation, or trapping of N in the core. Xenon is also depleted by one order of magnitude, and enriched in heavy isotopes relative to chondritic or solar Xe (the so-called “xenon paradox”). This depletion and isotope fractionation might have taken place due to preferential ionization of xenon by UV light from the early Sun, either before Earth's formation on parent material, or during irradiation of the ancient atmosphere. The second possibility is consistent with a recent report of chondritic-like Xe in Archean sedimentary rocks that suggests that this process was still ongoing during the Archean eon (Pujol et al., 2011). If the depletion of Xe in the atmosphere was a long-term process that took place after the Earth-building events, then the amounts of atmospheric ¹²⁹Xe and ^131–136Xe, produced by the short-lived radioactivities of ¹²⁹I (T_1/2 = 16 Ma) and ²⁴⁴Pu (T_1/2 = 82 Ma), respectively, need to be corrected for subsequent loss. Doing so, the I–Pu–Xe age of the Earth becomes ≤ 50 Ma after start of solar system formation, instead of ~ 120 Ma as computed with the present-day atmospheric Xe inventory.     

Rare gas constraints on hydrocarbon accumulation, crustal degassing and groundwater flow in the Pannonian Basin

The isotopic composition and abundances of He, Ne and Ar have been measured in a sequence of vertically stacked gas reservoirs at Hajduszoboszlo and Ebes, in the Pannonian Basin of Hungary. The gas reservoirs occur at depths ranging from 727 to 1331 m, are CH₄ dominated and occupy a total rock volume of approximately 1.5 km³. There are systematic variations in both major species abundances and rare gas isotopic composition with depth: CO₂ and N₂ both increase from 0.47 and 1.76% to 14.1 and 30.5%, respectively, and ⁴⁰Ar/³⁶Ar and ²¹Ne/²²Ne increase systematically from 340 and 0.02990 at 727 m to 1680 and 0.04290 at 1331 m. A mantle-derived He component between 2 and 5% is present in all samples, the remainder is crustal-radiogenic He. The Ar and Ne isotope variations arise from mixing between atmosphere-derived components in groundwater, and crustally produced radiogenic Ar and Ne. The atmosphere-derived ⁴⁰Ar and ²¹Ne decreases from 85 and 97% of the total ⁴⁰Ar and ²¹Ne at 727 m to 18 and 68% at 1331 m. The deepest samples are shown to have both atmosphere-derived and radiogenic components close to the air-saturated water and radiogenic production ratios. The shallowest samples show significant fractionation of He/Ar and Ne/Ar ratios in atmosphere-derived and radiogenic rare gas components, but little or no fractionation of He/Ne ratios. This suggests that diffusive fractionation of rare gases is relatively unimportant and that rare gas solubility partitioning between CH₄ and H₂O phases controls the observed rare gas elemental abundances.The total abundance of atmosphere-derived and radiogenic rare gas components in the Hajduszoboszlo gas field place limits on the minimum volume of groundwater that has interacted with the natural gas, and the amount of crust that has degassed and supplied radiogenic rare gases. The radiogenic mass balance cannot be accounted for by steady state production either within the basin sediments or the basement complex since basin formation. The results require that radiogenic rare gases are stored at their production ratios on a regional scale and transported to the near surface with minimal fractionation. The minimum volume of groundwater required to supply the atmosphere-derived rare gases would occupy a rock volume of some 1000 km³ (assuming an average basin porosity of 5%), a factor of 670 greater than the reservoir volume. Interactions between groundwater and the Hajduszoboszlo hydrocarbons has been on a greater scale than often envisaged in models of hydrocarbon formation and migration.     

An isotope study of the accumulation mechanisms of high-sulfur gas from the Sichuan Basin,southwestern China

The mechanism of hydrogen sulfide (H₂S) generation plays a key role in the exploration and development of marine high-sulfur natural gas, of which the major targets are the composition and isotope characteristics of sulfur-containing compounds. Hydrocarbon source rocks, reservoir rocks, natural gases and water-soluble gases from Sichuan Basin have been analyzed with an online method for the content of H₂S and isotopic composition of different sulfur-containing compounds. The results of comparative analysis show that the sulfur-containing compounds in the source rocks are mainly formed by bacterial sulfate reduction (BSR), and the sulfur compounds in natural gas, water and reservoir are mainly formed by thermal sulfate reduction (TSR). Moreover, it has been shown that the isotopically reversion for methane and ethane in high sulfur content gas is caused by TSR. The sulfur isotopic composition of H₂S in natural gas is inherited from the gypsum or brine of the same or adjacent layer, indicating that the generation and accumulation of H₂S have the characteristics of either a self-generated source or a near-source.     

Microanalysis of nitrogen isotope abundances: association of nitrogen with noble gas carriers in Allende

Current research efforts to explore and account for the distribution of nitrogen isotope abundances in the ancient and present-day solar wind and in meteorites often require measurement of nitrogen abundances and isotopic compositions in very small samples of rare extraterrestrial materials. Isotopic analysis of ～ 1 μg of N₂ is possible with modern techniques of dynamic mass spectrometry, but even this high sensitivity is a limiting factor for certain critical samples. We have utilized a statistically operated mass spectrometer coupled to an ultrahigh vacuum gas extraction and processing system to lower this limit by approximately four orders of magnitude. Quantities of N₂ ranging from ～ 100 ng to < 100 pg are measurable with permil to percent precision in isotope ratios. Nitrogen and all noble gases evolved during stepwise combustion of fine-grained matrix material separated from the Allende meteorite have been meausred simultaneously in a pilot experiment using this technique. Isotopically heavy H-Xe (CCF-Xe) and isotopically light N are co-sited in a carbonaceous carrier phase, supporting a nucleosynthetic origin for¹⁵N-depleted nitrogen in Allende. The great isotopic uniformity of trapped Ar in all carrier phases indicates that simple, physical mass fractionation in gravitational escape of volatiles from the primitive nebula cannot have played a significant role in generating the nitrogen compositions observed in solar system matter.     

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.