The case for a martian origin of the shergottites: nitrogen and noble gases in EETA 79001

Nitrogen and noble gases were measured in samples of a glass inclusion and the surrounding basaltic matrix from the antarctic shergottite EETA 79001. A nitrogen component trapped in the glass, but not present in the matrix, has a δ¹⁵N value at least as high as +190‰. Ratios of⁴⁰Ar/¹⁴N and¹⁵N/¹⁴N in the glass are consistent with dilution of a martian atmospheric component (δ¹⁵N = 620 ± 160‰,⁴⁰Ar/¹⁴N= 0.33 ± 0.03) by either terrestrial atmosphere adsorbed on the samples or by indigenous nitrogen from the minerals of the rock. Trapped noble gases in the glass reproduce, within error, the elemental and isotopic compositions measured in Mars' atmosphere by Viking, and are in general agreement with previous measurements except for much lower abundances of neutron-generated krypton and xenon isotopes. The most reasonable explanation at the present time for the noble gas pattern and the isotopically heavy nitrogen is that a sample of martian atmosphere has been trapped in the EETA 79001 glass, and that this meteorite, and thus the shergottites and probably the nakhlites and chassignites as well, originated on Mars.Nitrogen in the non-glassy matrix of EETA 79001 amounts to less than 0.5 ppm and has a spallation-corrected δ¹⁵N value in the range 0 to ?20‰; it may reflect indigenous nitrogen in the basalt or a mixture of indigenous and adsorbed terrestrial nitrogen. Spallogenic noble gases yield single-stage exposure ages between 400,000 and 900,000 years, depending on irradiation geometry. Trapped argon may have an unusually low³⁶Ar/³⁸Ar ratio. Trapped krypton, except for a small excess at⁸⁰Kr, is smoothly mass-fractionated with respect to either terrestrial or chondritic Kr. The trapped xenon composition is consistent with addition of neutron-capture, radiogenic and fissiogenic isotopes to a base composition resembling terrestrial atmospheric Xe. The elemental⁸⁴Kr/¹³²Xe ratio of 25 is close to the terrestrial value and very different from the chondritic ratio.     

Nitrogen isotope geochemistry of basaltic glasses: implications for mantle degassing and structure?

The nitrogen isotope geochemistry of 15 basaltic glasses has been investigated using stepped heating and high sensitivity static vacuum mass spectrometry. At low temperature (< 600°C) the glasses release small amounts of nitrogen with δ¹⁵N_AIR, averaging −0.3‰, suggesting surficial adsorption of atmospheric nitrogen. At high temperature, usually with a maximum at 1000°C, indigenous nitrogen with a concentration ranging from 0.2 to 2.1 ppm is released. The δ¹⁵N values of this high temperature release show a wide range from −4.5‰ to +15.5‰. There is no correlation between N ppm and δ¹⁵N, and the samples apparently form 3 groups with distinctive δ¹⁵N. Six MORB glasses from the Mid-Atlantic Ridge, East Pacific Rise and Juan de Fuca Ridge define a group with δ¹⁵N = +7.5 ± 1.3‰. In contrast two Indian Ocean MORB glasses (Carlsberg Ridge and Gulf of Aden) gave negative δ¹⁵N averaging −3.2‰. Glasses from Loihi Seamount have high δ¹⁵N averaging +14.0 ± 1.0‰. Comparison of the δ¹⁵N data with the mantle models derived from helium and argon isotope studies suggests that the wide range in δ¹⁵N may reflect in part heterogeneities in the mantle related to its degassing history. It is possible, however, that magmatic degassing processes have also affected nitrogen isotopic compositions, and the data cannot yet be unambiguously interpreted in terms of source variations.     

Noble gas state of the ancient mantle as deduced from noble gases in coated diamonds

Cores and coats of five coated diamonds, one from Botswana and four from Zaire, were separately analyzed for their noble gases. Noble gases in the diamonds are essentially of a trapped origin, including radio- and nucleogenic components such as⁴He, ⁴⁰Ar, ²¹Ne_excess and excesses in Xe isotopes (129, 131–136). The fairly precise elemental and isotopic abundances allow us to infer the noble gas state in the ancient mantle. ²⁰Ne/²²Ne ratios are fairly constant (11.8 ± 0.4), and very close to that of SEP (solar energetic particle)-Ne, but distinctly different from the atmospheric ratio. ²¹Ne/²²Ne ratios range from 0.028 to 0.06, which is attributed to nucleogenic ²¹Ne from ¹⁸O(α, n)²¹Ne and ²⁴Mg(n, α)²¹Ne reactions. The difference in ²⁰Ne/²²Ne between atmosphere and mantle can be attributed to the hydrodynamic escape of hydrogen from the primitive atmosphere during the very early stage in the Earth's history. ³⁸Ar/³⁶Ar and Kr isotopic ratios are identical to the atmospheric values within 1%. After correction for ²³⁸U- or ²⁴⁴Pu-fission Xe, the ^131–136Xe abundance ratios are indistinguishable from atmospheric ratios. Lighter Xe isotopes (^124–128Xe) are also likely to be atmospheric, but a final conclusion must wait until better data are obtained.In a ¹³⁶Xe/¹³⁰Xe−¹²⁹Xe/¹³⁰Xe diagram, diamond data lie on the same line as defined for MORB. The observed identical correlation for both diamonds and MORB's appears to suggest that the progenitor of the excess^131–136Xe is ²⁴⁴Pu, but not²³⁸U, though the direct Xe isotopic measurements was not precies enough to decide unanimously the progenitor.     

Crustal neon: a striking uniformity

By combining data from a diverse suite of crustal fluid samples representing a broad geographical distribution, we have identified a well-defined nucleogenic (crustal) neon component. The neon is produced from (α, n) and (n, α) nuclear interactions involving nuclei of O, Mg, and F [1]. In the limiting case of ²⁰Ne/²²Ne = 0, the composition is: ²¹Ne/²²Ne = 0.47 ± 0.01 and ²¹Ne/⁴He = (0.46 ± 0.08) × 10⁻⁷. A crustal O/F ratio of 110 (atomic) calculated from the ²¹Ne/²²Ne ratio is 4–10 times less than the average crustal O/F ratio. The discrepancy can be accounted for by an enhanced O/F ratio within the 10–40 μm range of the U-Th-generated α-particles.     

Geothermal assessment of the island of ischia (southern Italy) from isotopic and chemical composition of the delivered fluids

The Ischia geothermal system is hosted by silicic rocks of the Quaternary Potassic Roman Province, in southern Italy. Exploration drilling down to 1156 m depth in the mid-1950s provided information on boiling profiles (up to 250°C) and on the depth and permeability of the potential reservoirs. Discharge fluid samples were collected and analyzed to define the inflow of surrounding seawater (C1 ranges from 2.5 to 20 g/kg) into the system.Analyses of samples from surface manifestations and shallow wells collected during 1983 and 1988 point to the existence of three distinct mixing regimes, involving three water components. A dishomogeneous body of diluted water (Cl less than 2.5 g/kg), that occurs at depths > 700 m and reequilibrates at 240°C at least, is overlain by an aquifer of groundwater variably mixed with variably seawater (Cl from 4 to 10 g/kg), which tends to reequilibrate at 160°C. Steam-heated waters locally develop and act as dilutants of the rising geothermal fluids.Dilution, mixing, and evaporation of the ascending chloride fluids are supported by oxygen and hydrogen isotopic data the thermal waters being enriched in ¹⁸O and D with respect to local meteoric water by up to 7 and 30‰, respectively. The relative composition of the major cations in thermal solutions was used to discriminate the two main groups of thermal waters, the reservoir temperatures of which are estimated from the Na/K-gethermometer. K-Mg geothermometer indicates reequilibration in near-surface conditions.The isotopic composition of the fumarolic steam varies from −7 to −12‰ in ∂⁸O and from − 35 to − 70‰ in ∂D, in agreement with a deep mixed fluid that boils adiabatically from 240 to 80°C. The deuterium content of the H₂O-H₂ pair gives enrichment factor of about 830‰, corresponding to equilibrium temperature conditions slightly higher than the surface boiling temperatures. The ∂¹³C of CO₂is almost constant at −4.5‰ (1δ=0.4), suggesting an important magmatic contribution, and the ∂¹⁸O values of CO₂appears to in equilibrium with accompanying steam at the measured temperatures.The CO₂/Ar and H₂/Ar chemical ratios have been used to derive aquifer temperatures, the values obtained being consistent with those of solute geothermometers.     

Ar–Ar age and thermal history of martian dunite NWA 2737

We report an ³⁹Ar–⁴⁰Ar age determination of a whole rock sample of the olivine-rich, martian meteorite Northwest Africa (NWA) 2737. Those extractions releasing 0–48% of the ³⁹Ar define an ³⁹Ar–⁴⁰Ar isochron age of 160–190 Ma, when evaluated in various ways. Higher temperature extractions show increasing ages that eventually exceed the reported Sm–Nd age of 1.42 Ga. At least part of this excess ⁴⁰Ar may have been shock implanted from the martian atmosphere. We considered two possible interpretations of the Ar–Ar isochron age, utilizing the measured Ar diffusion characteristics of NWA 2737 and a thermal model, which relates Ar diffusion to the size of a cooling object after shock heating. One interpretation, that ⁴⁰Ar was only partially degassed by an impact event ~ 11 Ma ago (the CRE age), appears possible only if NWA 2737 was shock-heated to temperatures > 600 °C and was ejected from Mars as an object a few 10 s of cm in diameter. The second interpretation, which we prefer, is that NWA experienced an earlier, more intense shock event, which left it residing in a warm ejecta layer, and a less intense event ~ 11 Ma ago, which ejected it into space. Our evaluation would require NWA 2737 to have been heated by this first event to a temperature of ~ 300–500 °C and buried in ejecta to a depth of ~ 1–20 m. These conclusions are compared to model constraints on meteorite ejection from Mars reported in the literature. The second, Mars-ejection impact ~ 11 Ma ago probably heated NWA 2737 to no more than ~ 400 °C. NWA 2737 demonstrates that some martian meteorites probably experienced shock heating in events that did not eject them into space.     

Strontium stable isotopes fractionate in the soil environments?

This study shows that the stable isotopic composition of strontium (the ⁸⁸Sr/⁸⁶Sr ratio expressed as δ^88/86Sr value relative to the NBS987 standard) varies significantly in sedimentary terrestrial environments. The abundances of ⁸⁶Sr, ⁸⁸Sr isotopes were analyzed by MC-ICP-MS “Nu Plasma”. All studied rocks and waters show δ^88/86Sr values that are distinctly different from the measured NBS987 standard (yielding 0.01 ± 0.05‰, all errors are reported as 2σ). Modern corals from the northern Gulf of Aqaba, Red Sea yielded significantly different value than seawater (δ^88/86Sr = 0.22 ± 0.07‰, compared to 0.35 ± 0.06‰, respectively), in an excellent correlation with the δ^88/86Sr analyses reported by Fietzke and Eisenhauer [Fietzke, J., Eisenhauer, A., 2006. Determination of temperature-dependent stable strontium isotopes (⁸⁸Sr/⁸⁶Sr) fractionation via bracketing standard MC-ICP-MS. Geochm. Geophys. Geosyst. 7 (no. 8)] on other coral samples. All carbonate samples that originated in the marine environment: corals (porites and acropora from the northern Gulf of Aqaba); Cretaceous limestone and runoff from the Judea Mountains as well as lacustrine evaporitic aragonite (Dead Sea); and Red Sea and Atlantic seawater yield an average δ^88/86Sr value of 0.26 ± 0.1‰. On the other hand, secondary materials (products of chemical weathering) from the terrestrial environment of the Judea Mountain such as terra rossa soil and speleothem calcite (that derives its Sr from the above-lying soil) yielded significantly lower δ^88/86Sr value of − 0.17 ± 0.06‰. This indicates that strontium isotopes fractionate in the soil environment calling for a possible development of strontium isotopes as a tracer for processes of chemical weathering and pedogenesis.     

Stable isotopes of helium, nitrogen and carbon in a coastal submarine hydrothermal system

Geothermal gases from submarine and subaerial hot springs in Ensenada, Baja California Norte, Mexico, were sampled for determination of gas chemistry and helium, nitrogen and stable carbon isotope composition. The submarine hot spring gas is primarily nitrogen (56.1% by volume) and methane (43.5% by volume), whereas nearby subaerial hot spring gases are predominantly nitrogen (95–99% by volume). The N₂/Ar ratios and σ ¹⁵N values of the subaerial hot spring gas indicate that it is atmospheric air, depleted in oxygen and enriched in helium. The submarine hot spring gas is most probably derived from marine sediments of Cretaceous age rich in organic matter. CH₄ is a major component of the gas mixture (σ ¹³C = −44.05%₀), with only minor amounts of CO₂ (σ¹³C= −10.46%₀). The σ¹⁵N of N₂ is + 0.2%₀ with a very high N₂/Ar ratio of 160. The calculated isotopic equilibra tion temperature for CH₄---CO₂ carbon exchange at depth in the Punta Banda submarine geothermal field is approximately 200°C in agreement with other geothermometry estimates. The ³He/⁴He ratios of the hot spring gases range from 0.3 to 0.6 times the atmospheric ratio, indicating that helium is predominantly derived from the radioactive decay of U and Th within the continental crust. Thus, not all submarine hydrothermal systems are effective vehicles for mantle degassing of primordial helium.     

Hydrothermal silica chimney fields in the Galapagos Spreading Center at 86°W

Silica chimneys were discovered in 1985 at 86°W in the rift valley of the Galapagos Spreading Center at 2600 m depth (“Cauliflower Garden”). The inactive chimneys lack any sulfides and consist almost entirely of amorphous silica (up to 96 wt.% SiO₂, opal-A); Fe and Mn oxides are minor constituents. Oxygen isotope data show that formation of the silica chimneys took place at temperatures between 32°C (+29.9‰ δ¹⁸O) and 42°C (+27.8‰ δ¹⁸O).Th/Udating reveals a maximum age of 1440 ± 300y. Amorphous silica solubility relations indicate that the silica chimneys were formed by conductive cooling of pure hydrothermal fluids or by conductive cooling of a fluid/seawater mixture. Assuming equilibrium with quartz at 500 bars, initial fluid temperatures of more than 175°C (i.e., a concentration of > 182 ppm SiO₂) were required to achieve sufficient supersaturation for the deposition of amorphous silica at 40°C and 260 bars. If the silica chimneys originate from the same or a similar fluid as higher-temperature ( < 300°C) sulfide-silica precipitates found nearby (i.e., 2.5 km away), then subsurface deposition of sulfides may have occurred.     

Isotope geochemistry of minerals and fluids from Newberry volcano, Oregon

Isotopic compositions were determined for hydrothermal quartz, calcite, and siderite from core samples of the Newberry 2 drill hole, Oregon. The δ¹⁵O values for these minerals decrease with increasing temperatures. The values indicate that these hydrothermal minerals precipitated in isotopic equilibrium with water currently present in the reservoirs. The δ¹⁸O values of quartz and calcite from the andesite and basalt flows (700–932 m) have isotopic values which require that the equilibrated water δ¹⁸O values increase slightly (− 11.3 to −9.2‰) with increasing measured temperatures (150–265°C). The lithic tuffs and brecciated lava flows (300–700 m) contain widespread siderite. Calculated oxygen isotopic compositions of waters in equilibrium with siderite generally increase with increasing temperatures (76–100°C). The δ¹⁸O values of siderite probably result from precipitation in water produced by mixing various amounts of the deep hydrothermal water (− 10.5 ‰) with meteoric water (− 15.5 ‰) recharged within the caldera. The δ¹³C values of calcite and siderite decrease with increasing temperatures and show that these minerals precipitated in isotopic equilibrium with CO₂ of about −8 ‰.The δ¹⁸O values of weakly altered (<5% alteration of plagioclase) whole-rock samples decrease with increasing temperatures above 100°C, indicating that exchange between water and rock is kinetically controlled. The water/rock mass ratios decrease with decreasing temperatures. The δ¹⁸O values of rocks from the bottom of Newberry 2 show about 40% isotopic exchange with the reservoir water.The calculated δ¹⁸O and δD values of bottom hole water determined from the fluid produced during the 20 hour flow test are −10.2 and −109‰, respectively. The δD value of the hydrothermal water indicates recharge from outside the caldera.     

Noble gas elemental and isotopic abundances in deep-sea trenches in the western Pacific

Noble gas elemental and isotopic abundances were measured in seven deep-sea water samples from five different sampling sites in the Nankai Trough, the Japan Trench and the Kuril Trench. The samples were obtained by the manned submersible “Nautile”. Most of the sampling sites are associated with clam colonies and/or fluid venting. Excesses both in³He/⁴He ratio and He concentration are observed in a seawater sample collected a few kilometers off the clam colonies which were found at a depth of 3830 m at the mouth of the Tenryu Canyon. Concentrations of noble gases (Ne, Ar, Kr and Xe) in this sample show progressive depletion from Ne to Xe relative to those in 1°C air-saturated seawater, which can be attributed to mixing of hot water ( 15°C) with cold ambient water ( 1°C). Isotopic compositions of Ne, Ar, Kr and Xe in this sample are atmospheric. These observations may reflect venting of hot pore water around the Tenryu Canyon. All the other samples show a significant excess in concentration of all noble gases relative to 1°C air-saturated seawater and the isotopic compositions are atmospheric. This excess of noble gas concentrations may appear to be air contamination in the samples. However, results of hydrocarbon analyses of the Kaiko samples imply that such large amount of air contamination is improbable. Decomposition of gas hydrate in deep-sea sediments is a more likely explanation for the observed excess of noble gas concentration.     

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

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

Radiogenic, fissiogenic and nucleogenic noble gases in zircons

The concentrations and isotopic compositions of argon, krypton and xenon have been determined in a grain size suite of zircons separated from pyroxene syenite of the Botnavatn Igneous Complex, southwestern Norway. The UPb systematics of these zircons has been studied previously.Kr and Xe are mixtures of fissiogenic gas from the spontaneous fission of²³⁸U and a component with atmospheric isotopic composition. From correlation diagrams the fissiogenic component is determined to be:⁸³Kr :⁸⁴Kr :⁸⁶Kr = (4.6 ± 1.3) : (11.0 ± 2.0) : 100 and¹²⁹Xe :¹³¹Xe :¹³²Xe :¹³⁴Xe :¹³⁶Xe = (0.6 ± 0.3) : (8.8 ± 0.2) : (56.8 ± 0.3) : (82.8 ± 0.4) : 100. The fissiogenic¹³⁶Xe/⁸⁶Kr is 6.0 ± 0.4.The Ar isotopic composition shows radiogenic⁴⁰Ar and a small excess of³⁸Ar. The excess³⁸Ar of about 1 × 10⁻¹¹ cm³ STP/g can be explained by reactions of α-particles with chlorine. Asymmetric fission of²³⁸U which has been postulated to cause argon isotope anomalies in U-rich minerals is unnecessary to explain the observed³⁸Ar concentrations.UXe ages are (1.19 ± 0.07) Ga, in agreement with UPb ages. However, if the recoil loss of fissiogenic Xe is considered the UXe ages of these zircons are about 1.53 Ga, which is comparable with the KAr ages and some RbSr ages observed in basement rocks in this region. The uncertainty of the product of fission yield times spontaneous fission decay constant of²³⁸U prevents to decide which age is the true crystallization age.     

He,Ne and Ar isotopic composition of Fe-Mn crusts from the western and central Pacific Ocean and implications for their genesis

The noble gas nuclide abundances and isotopic ratios of the upmost layer of Fe-Mn crusts from the western and central Pacific Ocean have been determined. The results indicate that the He and Ar nu- clide abundances and isotopic ratios can be classified into two types: low 3He/4He type and high 3He/4He type. The low 3He/4He type is characterized by high 4He abundances of 191×10-9 cm3·STP·g-1 on average, with variable 4He, 20Ne and 40Ar abundances in the range (42.8―421)×10-9 cm3·STP·g-1, (5.40―141)×10-9 cm3·STP·g-1, and (773―10976)×10-9 cm3·STP·g-1, respectively. The high 3He/4He samples are characterized by low 4He abundances of 11.7×10-9 cm3·STP·g-1 on average, with 4He, 20Ne and 40Ar abundances in the range of (7.57―17.4)×10-9 cm3·STP·g-1, (10.4―25.5)×10-9 cm3·STP·g-1 and (5354―9050)×10-9 cm3·STP·g-1, respectively. The low 3He/4He samples have 3He/4He ratios (with R/RA ratios of 2.04―2.92) which are lower than those of MORB (R/RA=8±1) and 40Ar/36Ar ratios (447―543) which are higher than those of air (295.5). The high 3He/4He samples have 3He/4He ratios (with R/RA ratios of 10.4―12.0) slightly higher than those of MORB (R/RA=8±1) and 40Ar/36Ar ratios (293―299) very similar to those of air (295.5). The Ne isotopic ratios (20Ne/22Ne and 21Ne/22Ne ratios of 10.3―10.9 and 0.02774―0.03039, respectively) and the 38Ar/36Ar ratios (0.1886―0.1963) have narrow ranges which are very similar to those of air (the 20Ne/22Ne, 21Ne/22Ne, 38Ar/36Ar ratios of 9.80, 0.029 and 0.187, respectively), and cannot be differentiated into different groups. The noble gas nuclide abundances and isotopic ratios, together with their regional variability, suggest that the noble gases in the Fe-Mn crusts originate primarily from the lower mantle. The low 3He/4He type and high 3He/4He type samples have noble gas characteristics similar to those of HIMU (High U/Pb Mantle)- and EM (Enriched Mantle)-type mantle material, respectively. The low 3He/4He type samples with HIMU-type noble gas isotopic ratios occur in the Magellan Seamounts, Marcus-Wake Seamounts, Marshall Island Chain and the Mid-Pacific Sea- mounts whereas the high 3He/4He type samples with EM-type noble gas isotopic ratios occur in the Line Island Chain. This difference in noble gas characteristics of these crust types implies that the MagellanSeamounts, Marcus-Wake Seamounts, Marshall Is- land Chain, and the Mid-Pacific Seamounts originated from HIMU-type lower mantle material whereas the Line Island Chain originated from EM-type lower mantle material. This finding is consistent with varia- tions in the Pb-isotope and trace element signatures in the seamount lavas. Differences in the mantlesource may therefore be responsible for variations in the noble gas abundances and isotopic ratios in the Fe-Mn crusts. Mantle degassing appears to be the principal factor controlling noble gas isotopic abundances in Fe-Mn crusts. Decay of radioactive isotopes has a negligible influence on the nuclide abundances and isotopic ratios of noble gases in these crusts on the timescale of their formation.     

Earthquake-induced variations in the composition of the water in the geothermal reservoir at Vulcano Island, Italy

During 1979–1989, variations were observed in the oxygen composition of the water contained in the geothermal reservoir at Vulcano Island, Italy.The reservoir water, that has a magmatic origin, showed an oxygen composition of +1.0±0.5‰ δ¹⁸O during periods without local tectonic earthquakes, and an oxygen composition of +3.4±0.5‰ δ¹⁸O after the highest-energy seismic activity that occurred recently near the island. A slight increase of the δ¹⁸O value in the reservoir water was also observed after a low-energy sequence of tectonic earthquakes that occurred at very shallow depth just beneath Vulcano Island. These ¹⁸O variations in the reservoir water are consistent with earthquake-induced increases in the contribution from high-temperature δ¹⁸O-rich magmatic condensate to the geothermal reservoir, and with subsequent decreases in the δ¹⁸O value due to ¹⁸O exchanges at the temporarily increased reservoir temperature during reactions between the highly reactive magmatic condensate and the local rocks.Only minor changes in the deuterium composition of the reservoir water occurred with time, as the δD value in the magmatic condensate released from the magma after major local earthquakes quickly approached the δD value of the water contained in the geothermal reservoir.Also the chloride concentration in the reservoir water appears to be linked to the contribution from the magmatic fluid. This chloride content seems not to have undergone major changes with time, as it may be buffered by temporary increases in the reservoir temperature up to values >300°C induced by major local earthquakes. This mechanism may possibly occur also in other magmatic–hydrothermal systems.     

Cosmogenic 21Ne exposure dating of young basaltic lava flows from the Newer Volcanic Province,western Victoria,Australia

Cosmogenic ²¹Ne was utilised to determine exposure ages of young subaerial basaltic lava flows from the Newer Volcanic Province, western Victoria, Australia. The ages (36–53 ka) determined from co-existing cosmogenic ²¹Ne and ³He in olivines separated from basalts are consistent within analytical uncertainties with ages previously determined by cosmogenic ³⁶Cl exposure dating. This paper illustrates the potential of cosmogenic neon exposure ages in studying the eruption, surface morphology, and erosion history of young volcanic rocks, which are difficult to date using other conventional methods, such as K-Ar or ⁴⁰Ar/³⁹Ar dating. The present study demonstrates that combined cosmogenic ³He and ²¹Ne dating, specifically measured cosmogenic ³He/²¹Ne ratios, on the same samples, is powerful for evaluating the validity of calculated cosmogenic ³He and ²¹Ne surface exposure ages.     

Rare gases,water, and carbon in kaersutites

Kaersutites from Kakanui, New Zealand and from three localities in the southwestern United States have been analyzed for rare gases, water and carbon to investigate the volatile signature of the sub-continental mantle. This study does not confirm the high ³He/⁴He and ²¹Ne/²²Ne ratios reported by Saito et al. [1] for the Kakanui kaersutite. Instead, a ³He/⁴He ratio of 6 R_A and atmospheric ²¹Ne/²²Ne ratios were measured which are consistent with our current knowledge of the earth's mantle. A low ⁴⁰Ar/³⁶Ar of 320 and more than 10^?8 cm³/g of ³⁶Ar confirms the argon results of Saito et al. and indicates that significant quantities of ³⁶Ar reside in this portion of the mantle. Kaersutites from the southwestern United States (Arizona) have a heterogeneous helium isotope signature, ranging from 8.8 R_A at San Carlos to 0.46 at Hoover Dam. All D/H ratios for the water in kaersutites (?56‰ to ?78‰) represent typical mantle values with no apparent correlation with ³He/⁴He. The correlation of increasing carbon content (140–400 ppm) with increasing δ¹³C (?24.5‰ to ?16.7‰) may reflect differences in the proportions of oxidized and reduced carbon in these samples.     

Hydrothermal vent waters at 13°N on the East Pacific Rise: isotopic composition and gas concentration

Gas concentrations and isotopic compositions of water have been measured in hydrothermal waters from 13°N on the East Pacific Rise. In the most Mg-depleted samples ( 5 × 10⁻³ moles/kg) the gas concentrations are: 3–4.5 × 10⁻⁵ cm³ STP/kg helium, 0.62–1.24 cm³ STP/kg CH₄, 10.80–16.71 × 10⁻³ moles/kg CO₂. The samples contain large quantities (95–126 cm³/kg) of H₂ and some carbon monoxide (0.26–0.36 cm³/kg) which result from reaction with the titanium sampling bottles. δ¹³C in methane and CO₂ (−16.6 to −19.5 and −4.1 to −5.5 respectively) indicate temperatures between 475 and 550°C, whereas δ¹³C_CO is compatible with formation by reduction of CO₂ on Ti at 350°C close to the sampling temperature.³He/⁴He are very homogeneous at (7.5 ± 0.1)R_A(³He/⁴He = 1.0 × 10⁻⁵) and very similar to already published data as well as CH₄/³He ratios between 1.4 and 2.1 × 10⁶.¹⁸O and D in water show enrichments from 0.39 to 0.69‰ and from 0.62 to 1.49‰ respectively. These values correspond to W/R ratios of 0.4–7. The distinct¹⁸O enrichments indicate that the isotopic composition of the oceans is not completely buffered by the hydrothermal circulations. The³He-enthalpy relationship is discussed in terms of both hydrothermal heat flux and³He mantle flux.     

S, O and Sr isotope systematics of active vent materials from the Mariana backarc basin spreading axis at 18°N

Stable isotope ratios of S, O and Sr have been measured for active vent materials which were first found and sampled in April 1987 from the Mariana backarc spreading axis at 18°N. Chimneys consisted mostly of barite with a lesser proportion of sulfide minerals such as sphalerite, galena, chalcopyrite and pyrite. Theδ³⁴S values of sphalerite and galena taken from several chimneys and various parts of a chimney showed a narrow range from 2.1 to 3.1‰, suggesting uniform conditions of fluid chemistry during chimney growth. The sulfur isotopic results imply a contribution of hydrogen sulfide reduced from seawater sulfate in the deep hydrothermal reaction zone, considering that fresh glasses of the Mariana Trough basalts haveδ³⁴S= −0.6 ± 0.3‰. Sulfur isotopic compositions of hydrogen sulfide in the high temperature vent fluids (δ³⁴S= 3.6–4.8‰) which are higher than those of the sulfide minerals suggest the secondary addition of hydrogen sulfide partially reduced from entrained seawater SO₄²⁻ at a basal part of the chimneys. This interpretation is consistent with theδ³⁴S values of barite (21–22‰) that are higher than those of seawater sulfate. The residence time of the entrained SO₄²⁻ was an order of an hour on a basis of oxygen isotopic disequilibrium of barite. Strontium isotopic variations of barite and vent waters indicated that Sr in barite was mostly derived from the Mariana Trough basalts with a slight contribution from Sr in circulating sea-water, and that 10–20% mixing of seawater with ascending hydrothermal fluids induced precipitation of barite at the sea-floor.     

O/O mapping and hydrogeology of a short-lived (≈10 years) fumarolic (>500°C) meteoric–hydrothermal event in the upper part of the 0.76 Ma Bishop Tuff outflow sheet, California

¹⁸O/¹⁶O data from the 200-m-thick, 0.76 Ma Bishop Tuff outflow sheet provide evidence for a vigorous, short-lived (≈10 years), high-temperature, fumarolic meteoric–hydrothermal event. This is proved by: (1) the juxtaposition in the upper, partially welded Bishop Tuff of low-¹⁸O groundmass/glass (δ¹⁸O=−5 to +3) with coexisting quartz and feldspar phenocrysts having magmatic δ¹⁸O values (+8.7±0.3; +7.5±0.3); and (2) the fact that these kinds of ¹⁸O/¹⁶O signatures correlate very well with morphological features and mapped zones of fumarolic activity. Profiles of δ¹⁸O with depth in the Bishop Tuff within the fumarole area define a 40- to 50-m-thick, low-¹⁸O, stratigraphic zone that is sandwiched between the essentially unwelded near-surface portion of the tuff and an underlying, densely welded black tuff that displays magmatic ¹⁸O/¹⁶O values. Shallow-dipping columnar joints and other fumarolic features (i.e., subhorizontal tubular conduits and steep fissures) correlate very well with these pervasively devitrified, low-¹⁸O zones. The base of the low-¹⁸O zone is extremely sharp (3‰ per meter) and is located directly above the transition from partially welded tuff to densely welded black tuff. The observed average whole-rock ¹⁸O-depletions within this low-¹⁸O zone are about 6–7‰, requiring meteoric water/rock ratios in excess of 0.24 in mass units. Rainfall on the surface of the tuff would not have been high enough to supply this much H₂O in the short lifetime of fumarolic activity, suggesting that some recharge must have been from groundwater flow through the upper part of the tuff, above the sloping (1°–5°) top of the impermeable lower zone. This is compatible with the observation that the fumarolic areas roughly correlate with the preeruptive regional drainage pattern. Some of this recharge may in part have been from the lake that filled Long Valley caldera, which was dammed by the Bishop Tuff up to the level of this boundary between the partially and densely welded zones (≈7000 ft, the elevation of the highest Long Valley Lake shorelines). Gazis et al. had previously shown that the 2.8-Ma intracaldera Chegem Tuff from the Caucasus Mountains exhibits exactly the same kind of ¹⁸O-signature that we have correlated with fossil fumaroles in the Bishop Tuff outflow sheet. Although not recognized as such by McConnell et al.; ¹⁸O/¹⁶O data from drill-hole samples from the intracaldera Bishop Tuff in Long Valley also display this characteristic ¹⁸O signature (i.e., analogous δ¹⁸O-depth profiles, as well as low-¹⁸O groundmass coexisting with high-¹⁸O feldspar phenocrysts). This fumarolic ¹⁸O/¹⁶O signature is observed to much greater depths (≈650–750 m) in the intracaldera tuffs (≈1500 m thick) than it is in the ≈200-m-thick Bishop Tuff outflow sheet (≈80 m depth).