Noble gas isotopic compositions and water/gas chemistry of soda springs from the islands of Bioko,São Tomé and Annobon,along with Cameroon Volcanic Line,West Africa

Chemical and isotopic compositions are reported for water, and CO₂ and noble gases in groundwater and soda springs from Bioko, Principé, São Tomé and Annobon, all islands located in the off-shore part of the Cameroon Volcanic Line in West Africa. The soda spring waters are of Ca–Mg–HCO₃ type, with δD and δ¹⁸O values that range from −20 to −8‰ and −5.4 to −2.7‰ respectively, indicative of a meteoric origin. CO₂ is the main gas species in the springs. δ¹³C–CO₂ values vary from −2.8 to −5.0‰, overlapping the observed mantle C range (−3 to −8‰). CO₂/³He ratios (3–9×10⁹) suggest that most C (∼90%) in the samples is derived from the mantle. Neon has atmospheric isotopic compositions, while Ar is slightly enriched in radiogenic ⁴⁰Ar. ³He/⁴He ratios (3.0 to 10.1×10⁻⁶ or 2.1 to 7.2R_a, where R_a is the atmospheric ratio of 1.4×10⁻⁶) are much higher than those for typical crustal fluids (∼10⁻⁸) but lower than those expected for fluids derived from ‘high-³He/⁴He’ hotspots like Loihi and Iceland. This precludes significant contributions of such fluids in the source regions of the gases, and by inference, in the magmatism of these oceanic islands. Alternatively, approximately 90% of the He in São Tomé gases is inferred to be derived from a source similar to the MORB source. The ³He/⁴He ratio for the Bioko gas (6.6×10⁻⁶) may be derived from a source with a higher time integrated (U+Th)/³He ratio than the MORB source.     

Origin of hydrogen-nitrogen gas seeps,Oman

Six gas samples were collected from five thermal springs in the Semail Nappe ophiolite and the calcareous (calcite and dolomite) Hajar Formation, northern Oman. The³He/⁴He,⁴He/²⁰Ne,⁴⁰Ar/³⁶Ar and³⁸Ar/³⁶Ar ratios, chemical compositions (H₂, N₂, CO₂, CH₄, O₂, Ar and He), and stable isotope compositions (δD_H2, δD_H2O, δ¹³C_CO2, δ¹³C_CH4, and δ¹⁵N_N2) are reported. Samples from the ophiolite region are significantly anoxic with major constituents of H₂, CH₄ and N₂, while those from calcite and dolomite regions are ordinary gas seeps, consisting of N₂, CO₂ and/or O₂. The former H₂-rich gas is characterized by relatively high³He/⁴He ratio (0.4–0.8 R_atm) with low He content (<5 ppm), atmospheric⁴⁰Ar/³⁶Ar ratio, low N₂/Ar ratio (<55) and high δ¹⁵N_N2 value (∼1 ‰). On the other hand, the latter N₂-rich gas shows relatively low³He/⁴He ratio (0.1–0.4 R_atm) with high He concentration (>300 ppm), slight radiogenic⁴⁰Ar/³⁶Ar ratio, high N₂/Ar ratio (77–97) and low δ¹⁵N_N2 value (<0‰). Observed δD_H2 value of −536‰ in H₂-rich gas is distinguished from the literature value of −699‰ in the ophiolite region, giving discrepant isotope formation temperatures.     

Apparent decoupling of the He and Ne isotope systematics of the Icelandic mantle: The role of He depletion, melt mixing, degassing fractionation and air interaction

We present new He-Ne data for geothermal fluids and He-Ne-Ar data for basalts from throughout the Icelandic neovolcanic zones and older parts of the Icelandic crust. Geothermal fluids, subglacial glasses, and mafic phenocrysts are characterized by a wide range in helium isotope ratios (³He/⁴He) encompassing typical MORB-like ratios through values as high as 36.8 R_A (where R_A = air ³He/⁴He). Although neon in geothermal fluids is dominated by an atmospheric component, samples from the northwest peninsula show a small excess of nucleogenic ²¹Ne, likely produced in-situ and released to circulating fluids. In contrast, geothermal fluids from the neovolcanic zones show evidence of a contribution of mantle-derived neon, as indicated by ²⁰Ne enrichments up to 3% compared to air. The neon isotope composition of subglacial glasses reveals that mantle neon is derived from both depleted MORB-mantle and a primordial, ‘solar’ mantle component. However, binary mixing between these two endmembers can account for the He-Ne isotope characteristics of the basalts only if the ³He/²²Ne ratio of the primordial mantle endmember is lower than in the MORB component. Indeed, the helium to neon elemental ratios (⁴He/²¹Ne∗ and ³He/²²Ne_s where ²¹Ne∗ = nucleogenic ²¹Ne and ²²Ne_s = ‘solar’-derived ²²Ne) of the majority of Icelandic subglacial glasses are lower than theoretical values for Earth’s mantle, as observed previously for other OIB samples. Helium may be depleted relative to neon in high-³He/⁴He ratio parental melts due to either more compatible behavior during low-degree partial melting or more extensive diffusive loss relative to the heavier noble gases. However, Icelandic glasses show higher ⁴He/⁴⁰Ar∗ (⁴⁰Ar∗ = radiogenic Ar) values for a given ⁴He/²¹Ne∗ value compared to the majority of other OIB samples: this observation is consistent with extensive open-system equilibrium degassing, likely promoted by lower confining pressures during subglacial eruptions of Icelandic lavas. Taken together, the He-Ne-Ar systematics of Icelandic subglacial glasses are imprinted with the overlapping effects of helium depletion in the high-³He/⁴He ratio parental melt, binary mixing of two distinct mantle components, degassing fractionation and interaction with atmospheric noble gases. However, it is still possible to discern differences in the noble gas characteristics of the Icelandic mantle source beneath the neovolcanic zones, with MORB-like He-Ne isotope features prevalent in the Northern Rift Zone and a sharp transition to more primitive ‘solar-like’ characteristics in central and southern Iceland.     

Noble gas study of HIMU and EM ocean island basalts in the Polynesian region

Noble gas isotopes of HIMU and EM ocean island basalts from the Cook-Austral and Society Islands were investigated to constrain their origins. Separated olivine and clinopyroxene (cpx) phenocrysts were used for noble gas analyses. Since samples are relatively old, obtained from the oceanic area and showing chemical zoning in cpx phenocrysts, several tests on sample preparation and gas extraction methods were performed. First, by comparing heating and crushing methods, it has been confirmed that the crushing method is suitable to obtain inherent magmatic noble gases without radiogenic and cosmogenic components which were yielded after eruption, especially for He and Ne analyses. Second, noble gas compositions in the core and the rim of cpx phenocrysts were measured to evaluate the zoning effect on noble gases. The result has been that noble gas concentrations and He and Ne isotope ratios are different between them. The enrichment of noble gases in the rim compared to the core is probably due to fractional crystallization. Difference of He and Ne isotope ratios is explained by cosmogenic effect, and isotope ratios of the trapped component seem to be similar between the rim and the core. Third, leaching test reveals no systematic differences in noble gas compositions between leached and unleached samples.³He/⁴He ratios of HIMU samples in the Cook-Austral Islands are uniform irrespective of phenocryst type (olivine and cpx) and age of samples (10–18 Ma), and lower (average 6.8 R_A) than those of the Pacific MORB. On the other hand, ³He/⁴He of EM samples in the Cook-Austral Islands are similar to MORB values. EM samples in the Society Islands show rather higher ³He/⁴He than MORB. Ne, Kr and Xe isotope ratios are almost atmospheric within analytical uncertainties. ⁴⁰Ar/³⁶Ar are not so high as those of MORB. Anomalous noble gas abundance pattern such as He and Ne depletion and Kr and Xe enrichment relative to atmospheric abundances was observed. Furthermore, Ne/Ar and Kr/Ar show correlation with some trace elemental ratios like La/Yb.Lower ³He/⁴He of HIMU than MORB values requires relatively high time-integrated (U + Th)/³He for the HIMU source, which suggests that the HIMU source was produced from recycled materials which had been once located near the Earth’s surface. Moreover, extreme noble gas abundance pattern and strong correlation of Ne/Ar and Kr/Ar with La/Yb indicate that the HIMU endmember is highly depleted in light noble gases and enriched in heavy noble gases. Such feature is not common to mantle materials and is rather similar to the noble gas abundance patterns of the old oceanic crust and sediment, which supports the model that the HIMU source originates from subducted oceanic crust and/or sediment.If the HIMU source corresponds to the oceanic crust which subducted at 1–2 Ga as suggested by Pb isotope studies, however, the characteristic ³He/⁴He of HIMU (6.8 R_A) would be too high because radiogenic ⁴He produced by U and Th decay should dramatically decrease ³He/⁴He. To overcome this problem, the He open system model is introduced which includes the effects of ⁴He production and diffusion between the HIMU source material and the surrounding mantle. This model favors that the HIMU source resides in the upper mantle, rather than in the lower mantle. Furthermore, this model predicts the thickness of the HIMU source to be in the order of 1 km.In contrast to low and uniform ³He/⁴He character of HIMU, ³He/⁴He of EM are rather variable. Entrainment of upper mantle material and/or a less-degassed component are required to explain the observed ³He/⁴He of EM in the Polynesian area. Participation of the less-degassed component would be related to the “superplume” below the Polynesian region.     

Helium and carbon gas geochemistry of pore fluids from the sediment-rich hydrothermal system in Escanaba Trough

Ocean Drilling Program (ODP) Leg 169, which was conducted in 1996 provided an opportunity to study the gas geochemistry in the deeper part of the sediment-rich hydrothermal system in Escanaba Trough. Gas void samples obtained from the core liner were analyzed and their results were compared with analytical data of vent fluid samples collected by a submersible dive program in 1988. The gas geochemistry of the pore fluids consisted mostly of a hydrothermal component and was basically the same as that of the vent fluids. The He isotope ratios (R/R_A=5.6–6.6) indicated a significant mantle He contribution and the C isotopic compositions of the hydrocarbons [δ¹³C(CH₄)=−43‰, δ¹³C(C₂H₆)=−20‰] were characterized as a thermogenic origin caused by hydrothermal activity. On the other hand, the pore fluids in sedimentary layers away from the hydrothermal fields showed profiles which reflected lateral migration of the hydrothermal hydrocarbons and abundant biogenic CH₄. Helium and C isotope systematics were shown to represent a hydrothermal component and useful as indicators for their distribution beneath the seafloor. Similarities in He and hydrocarbon signatures to that of the Escanaba Trough hydrothermal system were found in some terrestrial natural gases, which suggested that seafloor hydrothermal activity in sediment-rich environments would be one of the possible petroleum hydrocarbon generation scenarios in unconventional geological settings.     

CO2, 13C/12C and H2O variability in natural basaltic glasses: a study comparing stepped heating and ftir spectroscopic techniques

A comparison of two independent techniques was used to assess the homogeneity of CO₂ and H₂O concentrations in a number of natural basaltic glasses. Variations in carbon concentration and isotopic ratio were determined by comparison of stepped heating data obtained in two different laboratories. Dissolved volatile concentrations were also obtained by stepped heating and Fourier Transform Infrared (FTIR) spectroscopy. Replicate stepped heating analyses of a mid-ocean ridge basaltic glass show that the concentration and ¹³C/¹²C of bulk magmatic and dissolved CO₂ vary by less than ±10% and ±0.5‰, respectively. A similar degree of correlation is observed for replicate stepped heating analyses of Mariana Trough glasses conducted in two different laboratories. Dissolved CO₂ concentrations determined by stepped heating also correlate well with concentrations measured by FTIR spectroscopy. The correspondence of results obtained in these experiments provide an upper limit to the degree of natural variation in concentrations and isotopic ratios of these volatiles in basaltic glasses and suggest that intrinsic, magmatic carbon has a relatively homogeneous distribution in these glasses. Water concentrations determined through extraction by heating and FTIR also show excellent agreement.     

Hydrothermal He and CO2 at Wudalianchi intra-plate volcano,NE China

Chemical and isotopic compositions have been measured for CO₂-rich bubbling gases discharging from cold springs in Wudalianchi intra-plate volcanic area, NE China. Observed ³He/⁴He ratios (2–3 R_A) and δ¹³C values of CO₂ (−5‰ to −3‰) indicate the occurrence of a mantle component released and transferred to the surface by the Cenozoic extension-related magmatic activities. The CO₂/³He ratios are in wide range of (0.4–97 × 10⁹). Based on the apparent mixing trend in a ³He/⁴He and δ¹³C of CO₂ diagram from all published data, the extracted magmatic end-member in the Wudalianchi Volcano has ³He/⁴He, δ¹³C and CO₂/³He value of ∼3.2 R_A, ∼−4.6‰ and ∼6 × 10¹⁰, respectively. These values suggest that the volatiles originate from the sub-continental lithospheric mantle (SCLM) in NE China and represent ancient fluids captured by prior metasomatic events, as revealed by geothermal He and CO₂ from the adjacent Changbaishan volcanic area.     

Improving noble gas based paleoclimate reconstruction and groundwater dating using Ne/Ne ratios

The interpretation of noble gas concentrations in groundwater with respect to recharge temperature and fractionated excess gas leads to different results on paleo-climatic conditions and on residence times depending on the choice of the gas partitioning model. Two fractionation models for the gas excess are in use, one assuming partial re-equilibration of groundwater supersaturated by excess air (PR-model, Stute et al., 1995), the other assuming closed-system equilibration of groundwater with entrapped air (CE-model, Aeschbach-Hertig et al., 2000). In the example of the Continental Terminal aquifers in Niger, PR- and CE- model are both consistent with the data on elemental noble gas concentrations (Ne, Ar, Kr, and Xe). Only by including the isotope ratio ²⁰Ne/²²Ne it can be demonstrated that the PR-model has to be rejected and the CE-model should be applied to the data. In dating applications ³He of atmospheric origin (³He_atm) required to calculate ³H-³He water ages is commonly estimated from the Ne excess presuming that gas excess is unfractionated air (UA-model). Including in addition to the Ne concentration the ²⁰Ne/²²Ne ratio and the concentration of Ar enables a rigorous distinction between PR-, CE- and UA-model and a reliable determination of ³He_atm and of ³H-³He water ages.     

Rare gas isotopes and parent trace elements in ultrabasic-alkaline-carbonatite complexes, Kola Peninsula: identification of lower mantle plume component

During the Devonian magmatism (370 Ma ago) ∼20 ultrabasic-alkaline-carbonatite complexes (UACC) were formed in the Kola Peninsula (north-east of the Baltic Shield). In order to understand mantle and crust sources and processes having set these complexes, rare gases were studied in ∼300 rocks and mineral separates from 9 UACC, and concentrations of parent Li, K, U, and Th were measured in ∼70 samples. ⁴He/³He ratios in He released by fusion vary from pure radiogenic values ∼10⁸ down to 6 × 10⁴. The cosmogenic and extraterrestrial sources as well as the radiogenic production are unable to account for the extremely high abundances of ³He, up to 4 × 10⁻⁹ cc/g, indicating a mantle-derived fluid in the Kola rocks. In some samples helium extracted by crushing shows quite low ⁴He/³He = 3 × 10⁴, well below the mean ratio in mid ocean ridge basalts (MORB), (8.9 ± 1.0) × 10⁴, indicating the contribution of ³He-rich plume component. Magnetites are principal carriers of this component. Trapped ³He is extracted from these minerals at high temperatures 1100°C to 1600°C which may correspond to decrepitation or annealing primary fluid inclusions, whereas radiogenic ⁴He is manly released at a temperature range of 500°C to 1200°C, probably corresponding to activation of ⁴He sites degraded by U, Th decay.Similar ⁴He/³He ratios were observed in Oligocene flood basalts from the Ethiopian plume. According to a paleo-plate-tectonic reconstruction, 450 Ma ago the Baltica (including the Kola Peninsula) continent drifted not far from the present-day site of that plume. It appears that both magmatic provinces could relate to one and the same deep-seated mantle source.The neon isotopic compositions confirm the occurrence of a plume component since, within a conventional ²⁰Ne/²²Ne versus ²¹Ne/²²Ne diagram, the regression line for Kola samples is indistinguishable from those typical of plumes, such as Loihi (Hawaii). ²⁰Ne/²²Ne ratios (up to 12.1) correlate well with ⁴⁰Ar/³⁶Ar ones, allowing to infer a source ⁴⁰Ar/³⁶Ar ratio of about 4000 for the mantle end-member, which is 10 times lower than that of the MORB source end-member. In (³He/²²Ne)_PRIM versus (⁴He/²¹Ne)_RAD plot the Kola samples are within array established for plume and MORB samples; almost constant production ratio of (⁴He/²¹Ne)_RAD ≅ 2 × 10⁷ is translated via this array into (³He/²²Ne)_PRIM ∼ 10. The latter value approaches the solar ratio implying the non-fractionated solar-like rare gas pattern in a plume source.The Kola UACC show systematic variations in the respective contributions of in situ-produced radiogenic isotopes and mantle-derived isotopes. Since these complexes were essentially plutonic, we propose that the depth of emplacement exerted a primary control on the retention of both trapped and radiogenic species, which is consistent with geological observations. The available data allow to infer the following sequence of processes for the emplacement and evolution of Kola Devonian UACC: 1) Ascent of the plume from the lower mantle to the subcontinental lithosphere; the plume triggered mantle metasomatism not later than ∼700 to 400 Ma ago. 2) Metasomatism of the lithosphere (beneath the central part of the Kola Peninsula), including enrichment in volatile (e.g., He, Ne) and in incompatible (e.g., U, Th) elements. 3) Multistage intrusions of parental melts, their degassing, and crystallisation differentiation ∼370 Ma ago. 4) Postcrystallisation migration of fluids, including loss of radiogenic and of trapped helium. Based on model compositions of the principle terrestrial reservoirs we estimate the contributions (by mass) of the plume material, the upper mantle material, and the atmosphere (air-saturated groundwater), into the source of parent melt at ∼2%, 97.95%, and ∼0.05%, respectively.     

Carbon and helium isotopic ratios at Kusatsu-Shirane Volcano,Japan

We have measured the chemical compositions, He/Ne ratios, He and C isotopes of 14 gas samples collected from the crater lake, fumaroles and hot springs associated with Kusatsu-Shirane Volcano, Japan. The³He/⁴He ratio decreases with increasing distance from the central crater of the volcano to the sampling site whereas the δ¹³C value of CO₂ increases with the distance. This tendency suggests that high³He/⁴He-low δ¹³C magmatic gas is mixed with and/or diluted by low³He/⁴He-high δ¹³C crustal gas with increasing distance from the crater. Alternatively, the variation of δ¹³C values may be the result of isotope fractionation during migration since the isotope shift is relatively small. Based on the apparent mixing trend in a³He/⁴He-δ¹³C diagram, the magmatic He and CO₂ in the volcano may have a³He/⁴He ratio of 8 R_atm and a δ¹³C value of −3.2%, respectively. The CO₂/³He ratios show a positive correlation with temperature of fumaroles or hot springs, which may be caused by a difference of temperature dependencies of the solubilities between CO₂ and He.     

Dynamics of the Galapagos hotspot from helium isotope geochemistry

We have measured the isotopes of He, Sr, Nd and Pb in a number of lava flows from the Galapagos Archipelago; the main goal is to use magmatic helium as a tracer of plume influence in the western volcanoes. Because the Galapagos lava flows are so well preserved, it is also possible to measure surface exposure ages using in situ cosmic-ray-produced ³He. The exposure ages range from <0.1 to 580 Ka, are consistent with other chronological constraints, and provide the first direct dating of these lava flows. The new age data demonstrate the utility of the technique in this important age range and show that the western Galapagos volcanoes have been erupting distinct compositions simultaneously for the last ∼10 Ka. The magmatic ³He/⁴He ratios range from 6.9 to 27 times atmospheric (R_a), with the highest values found on the islands of Isabela (16.8 R_a for Vulcan Sierra Negra) and Fernandina (23 to 27 R_a). Values from Santa Cruz are close to typical mid-ocean ridge basalt values (MORB, of ∼9 R_a) and Pinta has a ³He/⁴He ratio lower than MORB (6.9 R_a). These data confirm that the plume is centered beneath Fernandina which is the most active volcano in the archipelago and is at the leading edge of plate motion. The data are consistent with previous isotopic studies, confirming extensive contributions from depleted asthenospheric or lithospheric mantle sources, especially to the central islands. The most striking aspect of the helium isotopic data is that the ³He/⁴He ratios decrease systematically in all directions from Fernandina. This spatial variability is assumed to reflect the contribution of the purest plume component to Fernandina magmatism, and shows that helium is a sensitive indicator of plume influence. The highest ³He/⁴He ratios are found in volcanoes with lowest Na₂O(8) and FeO(8), which may relate to source composition as well as degree and depth of melting. An excellent correlation is observed between ³He/⁴He and Nb/La, suggesting that the Galapagos plume source is characterized by high concentrations of Nb (and Ta). The major and trace element correlations demonstrate that helium is controlled by silicate melting and source variations rather than degassing and/or metasomatic processes. Although lavas with radiogenic isotopic compositions tend to have higher ³He/⁴He, the island-wide isotopic variability cannot be explained by simple two components mixing alone. The preferred model to explain the isotopic data includes a heterogeneous plume, centered at Fernandina, which undergoes polybaric melting, and spatial divergence and mixing with asthenospheric material at shallower depths. The unique regional pattern of the helium isotopic data suggests that helium is extracted more efficiently than other elements during the early stages of melting in the ascending plume.     

Helium isotopes in gases of Mineral Waters in the western Caucasus

The He isotope composition as an indicator of mantle-derived component was studied in gases from mineral springs, stratal waters, and mud volcanoes developed west of the Teberda River valley (10 objects) and two springs in the central segment of the Greater Caucasus orogen between the active El’brus and Kazbek volcanoes. In the western segment of the orogen, the values of ³He/⁴He = R_corr vary in the range of (46–114) × 10⁻⁸ = (0.33–0.81)R_atm, where R_atm =1.4 × 10⁻⁶ is the atmospheric ratio. They are substantially lower as compared with values in the vicinity of El’brus and Kazbek and close to those in samples from the central segment equal to (70–134) × 10⁻⁸ = (0.50–0.96)R_atm, as well as to the values previously recorded in the Caucasian Mineral Waters (CMW) area. Moreover, the content of ³He in them is notably higher as compared with its crustal radiogenic level characteristic of mud volcanoes in the Taman Peninsula, where R = (1.4–2.8) × 10⁻⁸ = (0.01–0.02)R_atm. Nitrogen-methane gas from northern piedmonts of the western Caucasus also contain nonatmogenic components, including the radiogenic ⁴⁰Ar (⁴⁰Ar/³⁶Ar = 900), “excess” nitrogen (∼87% of the total N₂ concentration in sample) and the mantle He. These data specify the distribution of mantle derivates along the orogen strike and age of intrusive magmatic activity in its different segments.     

Solubilities of noble gases in magnetite: implications for planetary gases in meteorites

Solubilities of noble gases in magnetite were determined by growing magnetite in a noble-gas atmosphere between 450 and 700°K. Henry's law is obeyed at pressures up to 10^?2 atm for He, Ne, Ar and up to 10^?5 atm for Kr, Xe, with the following distribution coefficients at 500° (cc STP g^?1 atm^?5): He 0.042, Ne 0.016, Ar 3.6, Kr 1.3, Xe 0.88, some 10²–10⁵ times higher than previous determinations on silicate and fluoride melts. Apparent heats of solution in kcal/mole are: He ?2.42 ±0.12, Ne ?2.20 ±0.10, Ar ?15.25 ±0.25, Kr ?13.0 ±0.3, Xe ?12-5 ± 0.5. These values, too, stand in sharp contrast with earlier determinations on melts which were small and positive, but are comparable to the values for clathrates. Presumably the gases are held in anion vacancies.Extrapolation of the magnetite data to the formation temperature of C1 chondrites, 360°K, shows that the Ar_p³⁶ content of Orgueil magnetite could be acquired by equilibrium solubility at a total nebular pressure of 4 × 10^?6 atm. In the absence of data for silicates (the principal host phase of planetary gas), an attempt is made to estimate the solubilities required to account for planetary gases in meteorites. These values do not appear grossly unreasonable in the light of the magnetite data, when structural differences between the two minerals are taken into account. It seems that equilibrium solubility may be able to account for four features of planetary gas: elemental ratios, amounts, correlations with other volatiles and retentive siting. It cannot account for the isotopic fractionation of planetary gas, however.     

Carbon and Noble Gas Isotopes in the Tengchong Volcanic Geothermal Area, Yunnan, Southwestern China

Carbon and noble gas isotope analyses are reported for bubbling gas samples from the Tengchong volcanic geothermal area near the Indo-Eurasian suture zone. All samples contain a resolvable component of mantle-derived 3He. Occurrence of mantle-derived 3He coincides with surface volcanism. However, 3He occurs over a larger geographic areathan do surface volcanics. δ13C values for CO2 and CH4 vary from -33.4‰ to 1.6 ‰ and from -52.8‰ to -2.8‰, respectively. He and C isotope systematics indicate that CO2 and CH4 in the CO2-rich gases originated predominantly from magmatic component mixed with crustal CO2 produced from carbonate. However, breakdown of organic matter and near-surface processes accounts for the CH4 and CO2 in N2-rich gases. 3He/4He ratio distribution pattern suggests that mantle-derived He and heat sources of high-temperature system in central Tengchong originate from a hidden magma reservoir at subsurface. CO2-rich gases with the highest 3He/4He ratio (5.2 Ra) may be representative of the     

Pillow lavas of the Sierra Leone test site,Mid-Atlantic Ridge, 5°–7°N: Sr-Nd isotope systematics,geochemistry, and petrology

Based on detailed petrological, geochemical, and isotope-geochemical study, fragments of fresh pillow lavas with chilled glass margins dredged at the Sierra-Leone test site in the axial MAR rift zone between 5° and 7°N correspond to MORB tholeiites, which are not primitive mantle melts but were differentiated in intermediate magmatic (intrusive) chambers. Small-scale geochemical and Sr-Nd isotope heterogeneities were established for the first time in the basalts and their glasses. It was shown that some samples show significant nonsystematic differences in the ⁸⁷Sr/⁸⁶Sr ratio between the basalts and their chilled glasses and less significant difference in ?_Nd; higher Sr ratios can be observed both in the glasses and basalts of the same lava fragments. No significant correlation is observed between the isotope characteristics of the samples and their geochemistry; it was also shown that seawater did not affect the Sr and Nd isotope composition of the chilled glasses of the studied pillow lavas. It is suggested that such differences in isotope ratios are related to a small-scale heterogeneity of the melts owing to incomplete homogenization during their rapid ascent to the surface. The heterogeneity of the basaltic melts is explained by their partial contamination by the older plutonic rocks (especially gabbroids) of the lower oceanic crust, through which they ascended to the ocean floor surface. The wider scatter of the Sr isotopic ratios relative to Nd is related to the presence of xenocrysts of calcic plagioclase; correspondingly, the absence of a Nd mineral carrier in the rocks results in less distinct Nd isotope variations. It was shown that all of the studied basalts define a single trend along the mantle correlation array in the Sr-Nd isotope diagram. The causes of this phenomenon remain unclear.     

Geochemistry of gas emanations: A case study of the Réunion Hot Spot,Indian Ocean

The results of analysis of natural emanations in Réunion Island show a clear magmatic origin for CO₂ and He, while N₂ and Ar are predominantly derived from the atmosphere. The distribution of magmatic gases in the Piton des Neiges massif fits the local volcanotectonic context well and suggests that the areas concerned are still subject to volcanic activity at depth. A simple method is proposed for correcting gas concentration and isotope composition for water degassing. In doing so, the isotope and elemental (C, He) composition of gases is homogeneous for the two volcanoes. The isotope ratio of He (12.5 ± 0.5R/Ra) in the present discharges is in agreement with the results of previous studies on rocks of various ages from the two volcanoes. The isotope ratio of C(δ¹³C= −5 ‰ to −4 ‰ vs PDB) and the C/³ He ratio (∼4 × 10⁹) are similar to those found in other Hot Spot volcanic systems such as Kilauea (Hawaii) and Hengill (Iceland). These similarities suggest comparable volatile history for the respective mantle sources, the main differences being in the relative proportions of radiogenic ⁴He. In detail, Hot Spots appear enriched in C having a light composition with respect to MORB, possibly due to the addition of a C-rich (e.g. subducted) component, in addition to a relatively undegassed, ³He-rich, component.     

Helium and carbon isotope systematics of natural gases from Taranaki Basin,New Zealand

The chemical and isotopic compositions of gases from hydrocarbon systems of the Taranaki Basin of New Zealand (both offshore and onshore) show wide variation. The most striking difference between the western and south-eastern groups of gases is the helium content and its isotopic ratio. In the west, the Maui gas is over an order of magnitude higher in helium concentration (up to 190 μmol mol⁻¹) and its ³He/⁴He ratio of 3.8 R_A (where R_A=the air ³He/⁴He ratio of 1.4×10⁻⁶) is approximately half that of upper mantle helium issuing from volcanic vents of the Taupo Volcanic Zone. In the SE, the Kupe South and most Kapuni natural gases have only a minor mantle helium input of 0.03–0.32 R_A and low total helium concentrations of 10–19 μmol mol⁻¹. The ³He/C ratio (where C represents the total carbon in the gas phase) of the samples measured including those from a recent study of on-shore Taranaki natural gases are generally high at locations where the surface heat flow is high. The ³He/CO₂ ratio of the Maui gases of 5 to 18×10⁻⁹ is higher than the MORB value of 0.2 to 0.5×10⁻⁹, a feature found in other continental basins such as the Pannonian and Vienna basins and in many high helium wells in the USA. Extrapolation to zero CO₂/³He and CO₂/C indicates δ¹³C(CO₂) values between −7 and −5‰ close to that of MORB CO₂. The remaining CO₂ would appear to be mostly organically-influenced with δ¹³C(CO₂) c.−15‰. There is some evidence of marine carbonate CO₂ in the gases from the New Plymouth field. The radiogenic ⁴He content (He_rad) varies across the Taranaki Basin with the highest He_rad/C ratios occurring in the Maui field. δ¹³C(CH₄) becomes more enriched in ¹³C with increasing He_rad and hydrocarbon maturity. Because ³He/⁴He is related to the ratio of mantle to radiogenic crustal helium and ³He/C is virtually constant in the Maui field, there is a correlation between R_C/R_A (where R_C=air-corrected ³He/⁴He) and δ¹³C(CH₄) in the Maui and New Plymouth fields, with the more negative δ¹³C(CH₄) values corresponding to high ³He/⁴He ratios. A correlation between ³He/⁴He and δ¹³C(CO₂) was also observed in the Maui field. In the fields adjacent to Mt Taranaki (2518 m andesitic volcano), correlations of some parameters, particularly CO₂/CH₄, C₂H₆/CH₄ and δ¹³C(CH₄), are present with increasing depth of the gas reservoir and with distance from the volcanic cone.     

Mineralogy,petrology, and oxygen isotopic composition of Northwest Africa 12379, metal-rich chondrite with affinity to ordinary chondrites

Northwest Africa (NWA) 12379 is a new metal-rich chondrite with unique characteristics distinguishing it from all previously described meteorites. It contains high Fe,Ni-metal content (∼ 70 vol.%) and completely lacks interchondrule matrix; these characteristics are typical only for metal-rich carbonaceous (CH and CB) and G chondrites. However, chondrule sizes (60 to 1200 μm; mean = 370 μm), their predominantly porphyritic textures, nearly equilibrated chemical compositions of chondrule olivines (Fa_18.1–28.3, average Fa_24.9±3.2, PMD = 12.8; Cr₂O₃ = 0.03 ± 0.02 wt.%; FeO/MnO = 53.2 ± 6.5 (wt.-ratio); n = 28), less equilibrated compositions of low-Ca pyroxenes (Fs_3.2–18.7Wo_0.2–4.5; average Fs_14.7±3.7Wo_1.4±1.3; n = 20), oxygen-isotope compositions of chondrule olivine phenocrysts (Δ¹⁷O ∼ 0.2–1.4‰, average ∼ 0.8‰), and the presence of coarse-grained Ti-bearing chromite, Cl-apatite, and merrillite, all indicate affinity of NWA 12379 to unequilibrated (type 3.8) ordinary chondrites (OCs). Like most OCs, NWA 12379 experienced fluid-assisted thermal metamorphism that resulted in formation of secondary ferroan olivine (Fa₂₇) that replaces low-Ca pyroxene grains in chondrules and in inclusions in Fe,Ni-metal grains. Δ¹⁷O of the ferroan olivine (∼ 4‰) is similar to those of aqueously-formed fayalite in type 3 OCs, but its δ¹⁸O is significantly higher (15–19‰, average = 17‰ vs. 3―12‰, average = 8‰, respectively). We suggest classifying NWA 12379 as the ungrouped metal-rich chondrite with affinities of its non-metal fraction to unequilibrated OCs and speculate that it may have formed by a collision between an OC-like body and a metal-rich body and subsequently experienced fluid-assisted thermal metamorphism. Trace siderophile element abundances and isotopic compositions (e.g., Mo, Ni, Fe) of the NWA 12379 metal could help to constrain its origin.     

Noble gases as proxies of mean ocean temperature: sensitivity studies using a climate model of reduced complexity

Past global mean ocean temperature may be reconstructed from measurements of atmospheric noble gas concentrations in ice core bubbles. Assuming conservation of noble gases in the atmosphere-ocean system, the total concentration within the ocean mostly depends on solubility which itself is temperature dependent. Therefore, the colder the ocean, the more gas can be dissolved and the less remains in the atmosphere. Here, the characteristics of this novel paleoclimatic proxy are explored by implementing krypton, xenon, argon, and N₂ into a reduced-complexity climate model. The relationship between noble gas concentrations and global mean ocean temperature is investigated and their sensitivities to changes in ocean volume, ocean salinity, sea-level pressure and geothermal heat flux are quantified. We conclude that atmospheric noble gas concentrations are suitable proxies of global mean ocean temperature. Changes in ocean volume need to be considered when reconstructing ocean temperatures from noble gases. Calibration curves are provided to translate ice-core measurements of krypton, xenon, and argon into a global mean ocean temperature change. Simulated noble gas-to-nitrogen ratios for the last glacial maximum are δKr_atm = ?1.10‰, δXe_atm = ?3.25‰, and δAr_atm = ?0.29‰. The uncertainty of the krypton calibration curve due to uncertainties of the ocean saturation concentrations is estimated to be ±0.3 °C. An additional ±0.3 °C uncertainty must be added for the last deglaciation and up to ±0.4 °C for earlier transitions due to age-scale uncertainties in the sea-level reconstructions. Finally, the fingerprint of idealized Dansgaard-Oeschger events in the atmospheric krypton-to-nitrogen ratio is presented. A δKr_atm change of up to 0.34‰ is simulated for a 2 kyr Dansgaard-Oeschger event, and a change of up to 0.48‰ is simulated for a 4 kyr event.     

Regional groundwater focusing of nitrogen and noble gases into the Hugoton-Panhandle giant gas field, USA

The Hugoton-Panhandle giant gas field, located across SW Kansas and the Texas and Oklahoma panhandles in the USA, is the case type example of high nitrogen concentrations in a natural gas being linked with high helium concentrations. We collected 31 samples from producing wells in a north-south traverse of the 350-km-long field. The samples reflect the previously observed north-south change in ⁴He/N₂, with values changing from 0.020 to 0.049 respectively. ³He/⁴He, ²¹Ne/²²Ne, and ⁴⁰Ar/³⁶Ar vary between 0.14-0.25 Ra, 0.0373-0.0508, and 818-1156 respectively, and are caused by quantifiable contributions from mantle, crustal, and atmosphere-derived sources. The atmosphere-derived ²⁰Ne/³⁶Ar ratios are indistinguishable from groundwater values. The crustal ⁴He/²¹Ne* and ⁴He/⁴⁰Ar* ratios show a 60% excess of ⁴He compared to predicted production ratios in the crust and are typical of noble gases released from the shallow crust. The mantle ³He/N₂ and groundwater-recharge ³⁶Ar/N₂ ratios enable us to rule out significant magmatic or atmosphere contributions to the gas field N₂, which is dominantly crustal in origin.Correlated ²⁰Ne/N₂ and ⁴He/N₂ shows mixing between two distinct crustal N₂ components. One N₂ component (N₂*) is associated with the crustal ⁴He and groundwater-derived ²⁰Ne, and the other with no resolvable noble gas contribution. Measured δ¹⁵N_N2 values vary from +2.7‰ to +9.4‰. The N₂* and non-He-associated N₂ endmembers are inferred to have δ¹⁵N_N2 = −3‰ and +13‰ and contribute from between 25-60% and 75-40% of the nitrogen respectively. The non-He-associated nitrogen is probably derived from relatively mature organic matter in the sedimentary column. The δ¹⁵N_N2* value is not compatible with a crystalline or high-grade metamorphic source and, similar to the ⁴He, is inferred to be from a shallow or low metamorphic-grade source rock. ⁴He mass balance requires a regional crustal source, its association with significant magmatic ³He pointing to a tectonically active source to the west of the Hugoton system. The volume of groundwater required to source the ²⁰Ne in the gas field demonstrates the viability of the groundwater system in providing the collection, transport, and focusing mechanism for the ⁴He and N₂*. The N₂*/²⁰Ne ratio shows that the N₂* transport must be in the aqueous phase, and that the degassing mechanism is probably contact between the regional groundwater system and the preexisting reservoir hydrocarbon gas phase.