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.     

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 data from Goldfield and Tonopah epithermal Au-Ag deposits,ancestral Cascades Arc,USA: Evidence for a primitive mantle volatile source

The He, Ne, and Ar isotopic composition of fluid inclusions in ore and gangue minerals were analyzed to determine the source of volatiles in the high-grade Goldfield and Tonopah epithermal Au-Ag deposits in southwestern Nevada, USA. Ar and Ne are mainly atmospheric, whereas He has only a minor atmospheric component. Corrected ³He/⁴He ratios (with atmospheric He removed) range widely from 0.05 to 35.8 times the air ³He/⁴He ratio (R_A), with a median of 1.43 R_A. Forty-one percent of measured ³He/⁴He ratios are ≥4 R_A, corresponding to ≥50% mantle He assuming a mantle ratio of 8 R_A. These results suggest that mafic magmas were part of the magmatic-hydrothermal system underlying Goldfield and Tonopah, and that associated mantle-sourced volatiles may have played a role in ore formation. The three highest corrected ³He/⁴He ratios of 17.0, 23.7, and 35.8 R_A indicate a primitive mantle He source and are the highest yet reported for any epithermal-porphyry system and for the Cascades arc region. Compiled ³He/⁴He measurements from epithermal-porphyry systems in subduction-related magmatic arcs around the world (n = 209) display a statistically significant correlation between ³He/⁴He and Au-Ag grade. The correlation suggests that conditions which promote higher fluid inclusion ³He/⁴He ratios (abundance of mantle volatiles and focused upward volatile transport) have some relation to conditions that promote higher Au-Ag grades (focused flow of metal-bearing fluids and efficient chemical traps). Results of this and previous investigations of He isotopes in epithermal-porphyry systems are consistent with the hypothesis posed in recent studies that mafic magmas serve an important function in the formation of these deposits.     

Primary and secondary processes constraining the noble gas isotopic signatures of carbonatites and silicate rocks from Brava Island: evidence for a lower mantle origin of the Cape Verde plume

We present and discuss noble gas compositions of minerals from silicate rocks (olivines) and carbonatites (apatites and calcites) from Brava Island. The presence of an almost ubiquitous atmosphere-derived fingerprint is explained as reflecting contamination by seawater. Because of the high U and Th content in apatites, which are responsible for ⁴He production by α-decay, the high measured ⁴He/³He ratios do not represent magmatic signatures. In contrast, low values of ⁴He/³He in calcites (≥61,223; R/R _a ≤ 11.80) and olivines (≥56,240; R/R _a ≤ 12.85) are considered to be representative of signatures trapped at the time of crystallization, given that there are no evidences for significant cosmogenic additions. These relatively low ⁴He/³He ratios depicted by silicate and carbonatite rocks imply the contribution of a reservoir that evolved under low (U + Th)/³He; this is considered a strong evidence for the genesis of Brava by a mantle plume deeply anchored in the lower mantle. The inferred low ⁴He/⁴⁰Ar* ratio (≈0.3), before degassing, is thought to reflect the contribution to the carbonatites source of a mantle domain evolving under high K/U, which cannot be explained by recycling of crustal components. The possible link between the low ⁴He/⁴⁰Ar* source and the “missing Ar reservoir” is discussed. The usually referred geochemical dichotomy between Northern and Southern Cape Verde islands, which is markedly evident from Sr, Nd, and Pb isotope signatures, is not apparent from Brava Island (Southern Cape Verde), where some samples present relatively unradiogenic ⁴He/³He signatures, similar to those reported for the Northern islands of the archipelago.     

Emplacement age and thermal footprint of the diamondiferous Ellendale E9 lamproite pipe, Western Australia

The diamondiferous Ellendale 9 (E9) pipe is a funnel-shaped maar-diatreme volcano consisting of inward-dipping tuff sequences intruded by lamproite plugs and dykes. The host rocks for the E9 pipe are Permian sandstones. The multiple lithological contacts exposed within the mined maar volcano provide a natural laboratory in which to study the effect of volcanic processes on U–Th–Pb–He systematics. Zircon from the regional sandstone and E9 lamproite display a bimodal distribution of ages on (U–Th)/He–U/Pb plots. The zircon U/Pb ages for the E9 pipe (n?=?52) range from 440 to 2,725 Ma, while the cluster of (U–Th)/He ages for the lamproite dyke zircon indicate that dyke emplacement occurred at 20.6?±?2.8 Ma, concordant with a maximum emplacement age of about ≤22 Ma from phlogopite ⁴⁰Ar/³⁹Ar. These ages indicate a xenocrystic origin for the zircon entrained in the E9 dyke. The U/Pb ages of detrital zircon from the regional sandstone host (373–3,248 Ma; n?=?41) are indistinguishable from those of the lamproite zircon xenocrysts, whereas the detrital zircon in the host sandstone yield (U–Th)/He ages from 260 to 1,500 Ma. A thermochronology traverse across the E9 lamproite dyke reveals that the zircon (U–Th)/He ages in the host sandstone have not been significantly thermally reset during dyke emplacement, even at the contact. The capability of the zircon (U–Th)/He method to distinguish deep, mantle source lithologies from upper crustal source lithologies could be used in geochemical exploration for diamonds. Pre-screening of detrital samples using etching and helium assay methods will improve the efficiency and decrease the cost of greenfields exploration.     

Helium–carbon relationships in geothermal fluids of western Anatolia,Turkey

We investigate the helium, carbon and oxygen–hydrogen isotopic systematics and CO₂/³He ratios of 8 water and 6 gas samples collected from 12 geothermal fields in western Anatolia (Turkey). ³He/⁴He ratios of the samples (R) normalized to the atmospheric ³He/⁴He ratio (R_A = 1.39 × 10^? 6) range from 0.27 to 1.67 and are significantly higher than the crustal production value of 0.05. Fluids with relatively high R / R_A values are generally found in areas of significant heat potential (K?z?ldere and Tuzla fields). CO₂/³He ratios of the samples, ranging from 1.6 × 10⁹ to 2.3 × 10¹⁴, display significant variation and are mostly higher than values typical of an upper mantle source (2 × 10⁹). The δ¹³C (CO₂) and δ¹³C (CH₄) values of all fluids vary from ? 8.04 to + 0.35‰ and ? 25.80 to ? 23.92‰ (vs. PDB), respectively. Stable isotope values (δ¹⁸O–δD) of the geothermal waters are conformable with the Mediterranean Meteoric Water Line and indicate a meteoric origin. The temperatures calculated by gas geothermometry are significantly higher than estimates from chemical geothermometers, implying that either equilibrium has not been attained for the isotope exchange reaction or that isotopic equilibration was disturbed due to gas additions en route to the surface.Evaluation of He–CO₂ abundances indicates that hydrothermal degassing and calcite precipitation (controlled probably by adiabatic cooling due to degassing) significantly fractionate the elemental ratio (CO₂/³He) in geothermal waters. Such processes do not affect gas phase samples to anywhere near the same extent. For the gas samples, mixing between mantle and various crustal sources appears to be the main control on the observed He–C systematics: however, crustal inputs dominate the CO₂ inventory. Considering that limestone is the main source of carbon (～ 70 to 97% of the total carbon inventory), the carbon flux from the crust is found to be at least 20 times that from the mantle. As to the He-inventory, the mantle-derived component is found to vary up to 21% of the total He content and is probably transferred to the crust by fluids degassed from deep mantle melts generated in association with the elevated geotherm and adiabatic melting accompanying current extension. The range of ³He/enthalpy ratios (0.000032 to 0.19 × 10^? 12 cm³ STP/J) of fluids in western Anatolia is consistent with the release of both helium and heat from contemporary additions of mantle-derived magmas to the crust. The deep faults appear to have facilitated the deep circulation of the fluids and the transport of mantle volatiles and heat to the surface.     

An infrared investigation of inclusion-bearing diamonds from the Venetia kimberlite,Northern Province,South Africa : implications for diamonds from craton-margin settings

The Venetia kimberlites in the Northern Province of South Africa sampled diamonds from the lithosphere underlying the Central Zone of the Limpopo Belt. Given the general correlation of diamond-bearing kimberlites with old stable cratons, this tectonic setting is somewhat anomalous and, therefore, it is desirable to characterise the diamonds in terms of their infrared characteristics. A suite of diamonds of known paragenesis from the Venetia mine spans a large range of nitrogen concentrations from less than the detection limit to 1,355 ppm. Diamond nitrogen contents are, on average, higher in the eclogitic diamond population relative to the websteritic and peridotitic diamonds. Nitrogen aggregation states are variable, ranging from almost pure type IaA diamond (poorly aggregated nitrogen) to pure type IaB diamond (highly aggregated nitrogen). On a nitrogen aggregation diagram two distinct groups can be identified based on nitrogen content and nitrogen aggregation state. These are a minor population of diamonds with nitrogen contents generally higher than 500 ppm and nitrogen aggregation states of less than 40% IaB, and another, dominant population that is characterised by higher and more variable nitrogen aggregation. The unusually aggregated nature of the majority of the diamonds analysed is unique to Venetia relative to other intrusives on the Kaapvaal-Kalahari craton, but is similar to aggregation states observed for diamonds from other craton margin or adjacent mobile belt settings such as the Argyle lamproite and the George Creek kimberlite. This could be a consequence of diamond mantle residence at mantle temperatures higher than the norm for other kimberlites from the interior of cratons. Deformation of the mantle, associated with dynamic processes such as orogenesis or subduction, might also be responsible for accelerating the rate of nitrogen aggregation in these diamonds. Low numbers of diamonds with degradation of platelets at the Venetia kimberlite, relative to diamonds from the Argyle lamproite, indicate that deformation was at a significantly lower level. The comparatively low value of diamonds from Argyle (at approximately US8/carat) as opposed to Venetia (US8/carat) as opposed to Venetia (US90/carat) is in large part because of the very high abundance of brown diamonds at Argyle. Therefore, it is apparent that deformational history of the mantle in which the diamonds were resident prior to or during sampling by the host may have an important role to play in the profitability of a primary diamond deposit. The apparently consistent association of diamonds with unusually aggregated nitrogen with kimberlites, or lamproites intruded into craton margin or mobile belt settings suggests that it may be possible to recognise such contributory sources in alluvial diamond deposits, through the study of the infrared characteristics of the diamonds. Electronic supplementary material to this paper can be obtained by using the Springer Link server located at http://dx.doi.org/10.1007/s00410-002-0385-2     

Isotope-Geochemical Features and Genesis of Gases in the East Carpathian Region

The paper presents data on the composition of a gas phase of underground fluids in the East Carpathian region, including ³He/⁴He, ⁴⁰Ar/³⁶Ar, and ⁴He/²⁰Ne ratios. The argon isotope composition of these gases was used to estimate the fractions of atmospheric Aratm and radiogenic ⁴⁰Ar_rad formed in the rocks, N₂/Aratm ratio, and to reveal the admixture of nonatmogenic (“excess”) nitrogen in most samples. The CO₂ content in gases positively correlates with the fraction of mantle component in fluid helium. At the same time, the CO₂ content shows a negative correlation with the total helium (and light ³He enriching mantle derivatives), thus excluding the simultaneous influx of CO₂ and helium from a common mantle source in the fluids. A wide spectrum of ³He/⁴He = R in gases of the region spanning three orders of magnitude confirms the concept of mixing of the crustal and mantle components in the helium. However, even gases with similar R values show a wide scatter of He concentrations. This is mainly caused by the additional influx of other gases: CH₄ formed during OM transformation or CO₂ released during the thermal metamorphism of carbonate sequences. Correlation of the CH₄/³He ratio and the helium isotope composition in the Carpathian gases indicates the crustal origin of hydrocarbons, which formed economic gas pools in the Ciscarpathian Trough and the adjacent part of the Folded Carpathians. Lateral chemical and isotope variations revealed in the underground fluids are related to the tectonic zoning of the region. The helium isotope variations are also consistent with the geodynamic setting of the region (thinning of the crust and lithosphere towards the Pannonian Basin, growth of the background conductive heat flow and corresponding ascent of isotherms). In combination with geothermal data, they reflect specifics of the mantle heat-and-mass flow discharge.     

Atmospheric and juvenile noble gases in the Skaergaard layered igneous intrusion

Gabbro and diorite from the Skaergaard layered igneous intrusion contain noble gases which are mixtures of atmospheric and juvenile components. Atmospheric noble gases predominate in samples that have undergone extensive oxygen isotope exchange with meteoric-hydrothermal water. The source of the atmospheric noble gas component is inferred to be the hydrothermal circulation system. A juvenile component with ${}^{40}\text{Ar}{}^{36}\text{Ar}\text{≥ 6100}$ and containing fission xenon is also present This component predominates in samples showing unaltered magmatic oxygen isotope compositions. Neon of atmospheric isotopic composition is associated with the juvenile radiogenic ⁴⁰Ar and fission xenon. The source of this second noble gas component may be either the crustal country rock or the upper mantle. If the neon is juvenile primordial neon from a mantle source region, terrestrial primordial ${}^{20}\text{Ne}{}^{22}\text{Ne}$ is the same as atmospheric to within 4%. However, subduction of atmospheric noble gases into the upper mantle may provide an alternate source of neon and other noble gases in the mantle.     

He,Pb, Sr and Nd isotope constraints on magma genesis and mantle heterogeneity beneath young Pacific seamounts

Pb, Sr and Nd isotope variations are correlated in diverse lavas erupted at small seamounts near the East Pacific Rise. Tholeiites are isotopically indistinguishable from MORB (²⁰⁶Pb/²⁰⁴Pb=18.1–18.5; ⁸⁷Sr/⁸⁶Sr=0.7023–0.7028; ¹⁴³Nd/¹⁴⁴Nd=0.51326-0.51308); associated alkali basalts always show more radiogenic Pb and Sr signatures (²⁰⁶Pb/²⁰⁴Pb=18.8–19.2; ⁸⁷Sr/⁸⁶Sr=0.7029–0.7031) and less radiogenic Nd (¹⁴³Nd/¹⁴⁴Nd=0.51289–0.51301). The isotopic variability covers 80% of the variability for Pacific MORB, due to the presence of small-scale heterogeneity in the underlying mantle. Isotope compositions also correlate with trace element ratios such as La/Sm. Tholeiites at these seamounts have ³He/⁴He between 7.8–8.7 R _A(R _A= atmospheric ratio), also indistinguishable from MORB. He trapped in vesicles of alkali basalts, released by crushing in vacuo, has low ³He/⁴He (1.2–2.6 R)_Ain conjunction with low helium concentrations ([He]<5×10^–8 ccSTP/g). In many cases post-eruptive radiogenic ingrowth has produced He isotope disequilibrium between vesicles and glass in the alkali basalts; subatmospheric ³He/⁴He ratios characterize the He dissolved in the glass which is released by melting the crushed powders. The narrow range of ³He/⁴He in the vesicles of the alkali basalts suggests that low ³He/⁴He is a source characteristic, but given their low [He] and high (U + Th), pre-eruptive radiogenic ingrowth cannot be excluded as a cause for low inherited ³He/⁴He ratios. Pb, Sr and Nd isotope compositions in lavas erupted at Shimada Seamount, an isolated volcano on 20 m.y. old seafloor at 17°N, are distinctly different from other seamounts in the East Pacific (²⁰⁶Pb/²⁰⁴Pb=18.8–19.0, ⁸⁷Sr/ ⁸⁶Sr0.7048 and ¹⁴³Nd/¹⁴⁴Nd0.51266). Relatively high ²⁰⁷Pb/²⁰⁴Pb (15.6–15.7) indicates ancient (>2 Ga) isolation of the source from the depleted upper mantle, similar to Dupal components which are more prevalent in the southern hemisphere mantle. ³He/⁴He at Shimada Seamount is between 3.9–4.8 R _A. Because the helium concentrations range up to 1.5×10^–6, the low ³He/⁴He can not be due to radiogenic accumulation of ⁴He in the magma for reasonable volcanic evolution times. The low ³He/⁴He may be due to the presence of enriched domains within the lithosphere with high (U + Th)/He ratios, possibly formed during its accretion near the ridge. Alternatively, the low ³He/⁴He may be an inherent characteristic of an enriched component in the mantle beneath the East Pacific. Collectively, the He-Pb-Sr-Nd isotope systematics at East Pacific seamounts suggest that the range of isotope compositions present in the mantle is more readily sampled by seamount and island volcanism than by axial volcanism. Beneath thicker lithosphere away from the ridge axis, smaller degrees of melting in the source regions are less efficient in averaging the chemical characteristics of small-scale heterogeneities.     

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.     

Volatile composition of microinclusions in diamonds from the Panda kimberlite, Canada: Implications for chemical and isotopic heterogeneity in the mantle

In order to better investigate the compositions and the origins of fluids associated with diamond growth, we have carried-out combined noble gas (He and Ar), C and N isotope, K, Ca and halogen (Cl, Br, I) determinations on fragments of individual microinclusion-bearing diamonds from the Panda kimberlite, North West Territories, Canada. The fluid concentrations of halogens and noble gases in Panda diamonds are enriched by several orders of magnitude over typical upper mantle abundances. However, noble gas, C and N isotopic ratios (³He/⁴He = 4-6 Ra, ⁴⁰Ar/³⁶Ar = 20,000-30,000, δ¹³C = −4.5‰ to −6.9‰ and δ¹⁵N = −1.2‰ to −8.8‰) are within the worldwide range determined for fibrous diamonds and similar to the mid ocean ridge basalt (MORB) source value. The high ³⁶Ar content of the diamonds (>1 × 10⁻⁹ cm³/g) is at least an order of magnitude higher than any previously reported mantle sample and enables the ³⁶Ar content of the subcontinental lithospheric mantle to be estimated at ∼0.6 × 10⁻¹² cm³/g, again similar to estimates for the MORB source. Three fluid types distinguished on the basis of Ca-K-Cl compositions are consistent with carbonatitic, silicic and saline end-members identified in previous studies of diamonds from worldwide sources. These fluid end-members also have distinct halogen ratios (Br/Cl and I/Cl). The role of subducted seawater-derived halogens, originally invoked to explain some of the halogen ratio variations in diamonds, is not considered an essential component in the formation of the fluids. In contrast, it is considered that large halogen fractionation of a primitive mantle ratio occurs during fluid-melt partitioning in forming silicic fluids, and during separation of an immiscible saline fluid.     

Heterogeneous lithospheric mantle metasomatism in the eastern North China Craton: He–Ar isotopes in peridotite xenoliths from Cenozoic basalts

The abundances and isotopic compositions of Helium and Argon have been analyzed in a suite of fresh spinel peridotite xenoliths in Cenozoic basalts from the eastern North China Craton (NCC) by step-wise heating experiments, to investigate the nature of noble gas reservoirs in the subcontinental lithospheric mantle beneath this region. The xenoliths include one harzburgite collected from Hebi in the interior of the NCC, two lherzolites from Hannuoba at the northern margin of the craton, and three lherzolites from Shanwang and Nushan on the eastern margin. ³He/⁴He ratios in most of the xenoliths are similar to those of mid-ocean ridge basalts (MORB) or slightly lower (2–10.5 Ra, where Ra is the ³He/⁴He ratio of the atmosphere), suggesting mixing of MORB-like and radiogenic components. One olivine separate from Nushan has a helium value of 25.3 Ra, probably suggesting cosmogenic ³He addition. The ⁴⁰Ar/³⁶Ar ratios vary from atmospheric value (296) to 1625, significantly lower than the MORB value. Available data of the peridotite xenoliths indicate the He and Ar isotopic systematics of the mantle reservoirs beneath the NCC can be interpreted as mixtures of at least three end-members including MORB-like, radiogenic and atmospheric components. We suggest that the MORB-like noble gases were derived from the underlying asthenosphere during mantle upwelling, whereas the radiogenic and recycled components probably were incorporated into the lithospheric mantle during circum-craton subduction of oceanic crust. Available data suggest that the MORB-like fluids are better preserved in the interior of the NCC, whereas the radiogenic ones are more prevalent at the margins. The Paleo-Asian ocean subduction system probably was responsible for the enriched and recycled noble gas signatures on the northern margin of the craton, while the Pacific subduction system could account for the observed He–Ar isotopic signatures beneath the eastern part. Therefore, integration of helium and argon isotopes reflects heterogeneous metasomatism in the lithospheric mantle and demonstrates the critical importance of lithospheric mantle modification related to both circum-craton subduction of oceanic crust and asthenospheric upwelling beneath the eastern NCC.     

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.     

Diamondiferous peridotite xenoliths from the Argyle (AK1) lamproite pipe,Western Australia

This paper describes a suite of peridotite xenoliths. some carrying diamonds at high grades, from the richly diamondiferous early Proterozoic (1180 Ma) Argyle (AK1) lamproite pipe, in northwestern Australia. The peridotites are mostly coarse garnet lherzolites but also include garnet harzburgite, chromite — garnet peridotite, a garnet wehrlite, and an altered spinel peridotite with extremely Cr-rich chromite. In all cases the garnet has been replaced by a kelyphite-like, symplectic intergrowth of Alrich pyroxenes, Al-spinel and secondary silicates. The peridotites have refractory compositions characterized by high Mg/(Mg+Fe) and depletion in lithophile elements (Al₂O₃ and CaO < 1%, Na₂O0.03%) and high field strength cations such as Ti, Zr, Y, and Yb. Olivines have high Mg/(Mg+Fe) (Mg ^91–93 ) and, like olivine inclusions in diamonds from the Argyle pipe, contain detectable amounts of Cr₂O₃ (0.03%–0.07%) but have very low CaO contents (typically 0.04%–0.05%). Enstatites (Mg ^92–94 ) have comparatively high Cr₂O₃ (0.2%–0.45%) and Na₂O (up to 0.18%) but very low Al₂O₃ contents (0.5%–0.7%). Diopsides (Mg ^92–94 , Ca/(Ca+Mg+Fe)=0.37–0.43) are Cr-rich (0.7%–1.9% Cr₂O₃) and have low Al₂O₃ (0.7%–2.2%) and Na₂O (0.5%–1.6%) contents. Many have high K₂O contents, typically 0.1%–0.4% but up to 1.3% K₂O in one xenolith. The chromite coexisting with former garnet is Mg-and Cr-rich [Mg/(Mg+Fe²⁺)=0.68–0.72, Cr/(Cr+Al)=0.72–0.79] whereas chromite in the spinel peridotite is even more Cr-rich (65% Cr₂O₃, Cr/(Cr+Al)=0.85, resembling inclusions in diamond. One highly serpentinized former garnet peridotite contains a Cr-rich (up to 13% Cr₂O₃) titanate resembling armalcolite but containing significant K₂O (1%–2.5%), CaO (0.6%–2.2%), ZrO₂ (0.1%–0.8%), SrO (0.1%–0.3%), and BaO (up to 0.58%): this appears to have formed as an overprint of the primary mineralogy. Temperatures and pressures estimated from coexisting pyroxenes and reconstructed garnet compositions indicate that the garnet lherzolites equilibrated at 1140°–1290° C and 5.0–5.9 GPa (160–190 km depth), within the stability field of diamond. Oxygen fugacties within the diamond forming environment are estimated from spinel-bearing assemblages to be reducing, with f _O2 between MW and IW. The presence of significant K in the diopsides from the peridotite xenoliths and in diopsides from heavy mineral concentrate from the Argyle pipe implies metasomatic enrichment of the subcontinental lithosphere within the diamond stability field. The P-T conditions estimated for the Argyle peridotites demonstrate that diamondiferous lamproite magmas incorporate mantle xenoliths from similar depths to kimberlites in cratonic settings, and imply that Proterozoic cratonized orogenic belts can have lithospheric roots of comparable thickness to beneath Archaean cratons. These roots lie at the base of the lithosphere within the stability field of diamond. The xenoliths, the calcic nature of chrome pyropes from heavy mineral concentrate, and the diamond inclusion assemblage indicate that the lighosphere beneath the Western Australian lamproites is mostly depleted lherozolite rather than the harzburgite commonly found beneath Archaean cratons. Nevertheless, the dominance of eclogitic paragenesis inclusions in Argyle diamonds indicates a significant proportion of diamondiferous eclogite is also present. The form, mineral inclusion assemblage, and the C-isotopic composition of diamonds in the peridotite xenoliths suggest that disaggregated diamondiferous peridotites are the source of the planar octahedral diamonds which constitute a minor component of the Argyle production. These diamonds are believed to have formed from mantle carbon in reduced, refractory peridotite (Iherzolite-harzburgite) in contrast to the predominant strongly ¹³C-depleted eclogitic suite diamonds which contain a recycled crustal carbon component. The source region of the lamproites has undergone long-term (2 Ga) enrichment in incompatible elements.     

塔里木大火成岩省瓦吉里塔格霞石岩稀有气体同位素特征及其地质意义

稀有气体被广泛用作地球化学示踪剂,本文对塔里木大火成岩省西北缘瓦吉里塔格霞石岩中的橄榄石和辉石单矿物进行了稀有气体同位素测定。结果表明,瓦吉里塔格霞石岩中的橄榄石和辉石单矿物具有较低的~3He/~4He值(分别为2.0~2.4 Ra和0.65~0.85 Ra)和略高于大气值的~(40)Ar/~(36)Ar值(342.3~651.7),反映了由古板块俯冲导致的较低的He、Ar同位素比值特征。研究表明,早中古生代南天山洋向南俯冲到塔里木板块之下,将富U或富~4He以及含有大气组分的流体带入到深部地幔,在塔里木地幔柱的作用下地幔源区发生低程度部分熔融产生霞石岩岩浆。     

Noble gas tracing of groundwater/coalbed methane interaction in the San Juan Basin, USA

The San Juan Basin natural gas field, located in northwestern New Mexico and southwestern Colorado in the USA, is a case-type coalbed methane system. Groundwater is thought to play a key role in both biogenic methane generation and the CO₂ sequestration potential of coalbed systems. We show here how noble gases can be used to construct a physical model that describes the interaction between the groundwater system and the produced gas. We collected 28 gas samples from producing wells in the artesian overpressured high production region of the basin together with 8 gas samples from the underpressured low production zone as a control. Stable isotope and major species determination clearly characterize the gas in the high production region as dominantly biogenic in origin, and the underpressured low producing region as having a significant admix of thermogenic coal gas. ³He/⁴He ratios increase from 0.0836R_a at the basin margin to 0.318R_a towards the center, indicating a clear but small mantle He signature in all gases. Coherent fractionation of water-derived ²⁰Ne/³⁶Ar and crustal ⁴He/⁴⁰Ar* are explained by a simple Rayleigh fractionation model of open system groundwater degassing. Low ²⁰Ne concentrations compared to the model predicted values are accounted for by dilution of the groundwater-associated gas by desorbed coalbed methane. This Rayleigh fractionation and dilution model together with the gas production history allows us to quantify the amount of water involved in gas production at each well. The quantified water volumes in both underpressured and overpressured zones range from 1.7 × 10³ m³ to 4.2 × 10⁵ m³, with no clear distinction between over- and underpressured production zones. These results conclusively show that the volume of groundwater seen by coal does not play a role in determining the volume of methane produced by secondary biodegradation of these coalbeds. There is no requirement of continuous groundwater flow for renewing the microbes or nutrient components. We furthermore observe strong mass related isotopic fractionation of ²⁰Ne/²²Ne and ³⁸Ar/³⁶Ar isotopic ratios. This can be explained by a noble gas concentration gradient in the groundwater during gas production, which causes diffusive partial re-equilibration of the noble gas isotopes. It is important for the study of other systems in which extensive groundwater degassing may have occurred to recognize that severe isotopic fractionation of air-derived noble gases can occur when such concentration gradients are established during gas production. Excess air-derived Xe and Kr in our samples are shown to be related to the diluting coalbed methane and can only be accounted for if Xe and Kr are preferentially and volumetrically trapped within the coal matrix and released during biodegradation to form CH₄.     

Upwelling of Mantle-derived Material in Southeast China: Evidence from Noble Gas Isotopes

Shallow groundwater collected in Chaozhou,Huizhou,and Guangzhou allowed testing of concentrations and the isotope ratios of noble gases.Based on the calculated noble gas temperature(NGT)and the ratio of noble gas isotopes,the recharge temperature,recharge source,and residence time of groundwater can be calculated.In addition,the contribution of noble gas components from different sources to the sample components can be assessed.In the Huizhou area,according to the 1/Xe vs.Ne/Xe and NGT data,the shallow sandstone-confined water samples in the Shiba area and the unconfined water samples of the Huangshadong are in different temperature ranges,indicating that they have different recharge sources,both in time or space.The He components in the samples are calculated to obtain the content of radiogenic ⁴He in the crust and to simulate the groundwater ages.The noble gas isotope ratios show the addition of mantle components into the basalt aquifers and sandstone aquifers in Chaozhou and Huizhou.Except for atmospheric and crustal sources,there is a certain proportion of mantle-derived components in the shallow underground cold water in Huizhou and Chaozhou.The noble gases in the Chaozhou groundwater have an obvious mantle signature,allowing speculation that there is a deep fluid carrying mantle characteristics.This upwelling of mantle-derived material might be caused by the India-Eurasia collision or that between the Philippine Sea Plate and the Eurasian Plate.     

Combined Li-He isotopes in Iceland and Jan Mayen basalts and constraints on the nature of the North Atlantic mantle

Lithium (Li) isotopes are thought to provide a powerful proxy for the recycling of crustal material, affected by low temperature alteration, through the mantle. We present Li isotope compositions for basaltic volcanic rocks from Hengill, Iceland, and Jan Mayen in order to examine possible links between ocean island volcanism and recycled oceanic crust and to address recent suggestions that mantle ³He/⁴He is also related to recycling of ancient slabs. Basaltic glasses spanning a range of chemical enrichment from the Hengill fissure system define an inverse correlation between δ⁷Li (3.8-6.9‰) and ³He/⁴He (12-20 R_A). The high-³He/⁴He basalts have low δ¹⁸O as well as excess Eu and high Nb/U, but carry no Li isotope evidence of being the product of recycling of altered slab or wedge material. In fact, there is no clear correlation between Li or He isotopes on the one hand and any of the other fingerprints of recycled slab components. The low-³He/⁴He samples do have elevated Nb/U, Sr/Nd, positive Eu anomalies and high δ⁷Li (∼6.9‰), providing evidence of a cumulate-enriched source that could be part of an ancient altered ocean floor slab.Basalts from Jan Mayen are characterized by large degrees of enrichment in incompatible trace elements typical of EM-like basalts but have homogeneous δ⁷Li typical of depleted mantle (3.9-4.7‰) providing evidence for a third mantle source in the North Atlantic. It appears that oceanic basalts can display a wide range in isotope and trace element compositions associated with recycled components whilst exhibiting no sign of modern surface-altered slab or wedge material from the Li isotope composition.     

Isotopic Geochemistry of Non—hydrocarbons in Natural Gases from the Sanshui Basin,Guangdong Province,China

This study is focused on geothermal heat flow and the origin of non-hydrocarbons in natural gases in terms of the isotope geochemical characteristics of Ar, He, CO₂ and N₂ in natural gases from the Sanshui Basin, Guangdong Province. China.³He/⁴He ratios are of (1.60-6.39) × 10^-6, and⁴⁰Ar/³⁶Ar ratios of 450–841. The carbon isotopic composition (δ_l3C PDB) of carbon dioxide ranges from -20‰ to -2‰. δ^l5N(air) ratios have a wider range of-57 ‰- +95 ‰. The isotope geochemical characteristics of non-hydrocarbons indicate that He, Ar and N₂ in the gas reservoirs enriched in non-hydrocarbons were derived largely from the upper mantle. Non-hydrocarbons in gaseous hydrocarbon reservoirs consist mainly of crustal radiogenic He and⁴⁰Ar and some mantle-derived He and Ar, as well as of¹³C-depleted carbon dioxide and nitrogen generated as a result of thermal decomposition of organic matter in strata. Carbon dioxide enriched in¹³C was derived largely from carbonate rocks and partially from the lower crust and upper mantle. Based on the relationship between geothermal heat flow (Q) and³He/⁴ He ratio in natural gases, the Q values for the area studied have been calculated. Similar Q values are reported from the upper mantle uplift area (77 mWm^-2) in Huabei and the Tancheng-Lujiang Rift Zone (88 mWm^-2). More than 60 percent of geothermal heat flow in the Sanshui Basin may have been derived from the upper mantle. The project is financially supported by the National Natural Science Foundation of China.