Sources of radiogenic helium in a clay till aquitard and its use to evaluate the timing of geologic events

Concentrations of dissolved gases (He, Ne, Ar and N₂) were measured in pore waters collected from a Pleistocene (0-80 m depth) and Cretaceous (80-156 m depth) aged, clay-rich, aquitard system using both a conventional copper-tube method and in situ diffusion samplers. Both methods yielded similar results. He data revealed a well-defined increase in concentration with depth, from 1.7 × 10⁻⁸ cm³ He STP g⁻¹ water near the water table (at 2.3 m below ground surface) to 6.9 × 10⁻⁶ cm³ He STP g⁻¹ water at ∼80 m below ground surface (B.G.) The concentration at depth greatly exceeded values for atmospheric solubility at in situ temperatures and could not be attributed to steady-state production from α-decay of U and Th within the aquitard system. Trends in He isotope ratios and concentrations suggest accumulation as a result of both release of residual ⁴He from within the Pleistocene clay-rich till (ca. 87%) and an ascending radiogenic helium flux from underlying Cretaceous-age sediments (ca. 13%). One-dimensional transport modeling of the He data suggests that between 15 ka and 25 ka were required to produce the observed profile. This time frame agrees with studies utilizing isotope tracers (i.e., D/H and ¹⁴C-DIC) to estimate the timing of deposition for the till at this site. Our results demonstrate the utility of using helium, a nonreactive tracer, for delineating hydrogeologic processes in slow permeability geologic strata, and also support the contention that thick clay-rich surficial aquitards can provide long-term containment of contaminants, including hazardous wastes.     

Helium and argon isotopes in spinel lherzolite from Damaping, northern Zhangjiakou

Spinel lherzolite found in Damaping, northern Zhangjiakou, Hebei Province occurs as xenoliths in the Hannuoba basalts that consist of alkali basalt and tholeiite. Spinel lherzolites contain 50%–70% olivine (Fo: 90%), 10%–20% clinopyroxene (predominantly Di), 10%–30% orthopyroxene (predominantly En), and less than 5% spinel.³He/⁴He and⁴⁰Ar/³⁸Ar ratios in the olivine are 7.56×10⁻⁷ and 299.1, respectively.³He/⁴He and⁴⁰Ar/³⁸Ar ratios in the orthopyroxene (enstatite) are 9.1×10⁻⁷ and 307, respectively. Olivine grains are fractured irregularly, and pyroxene grains characterized by well developed cleavages, which would have resulted from explosion during the rapid eruption of lava from the deep interior to the surface. The lower isotope ratios of helium and argon may indicate that the spinel lherzolite xenoliths were derived from the strongly degassed and depleted upper mantle, and that the mantle is inhomogeneous.³He losses to some extent might affect the helium isotope ratios. The project was financially supported by the National Natural Science Foundation of China (No. 49273185).     

Diffusion kinetics of proton-induced Ne, He, and He in quartz

A natural quartz sample free of mineral and fluid inclusions was irradiated with a 200 MeV proton beam to produce spallogenic ²¹Ne, ³He and ⁴He. Temperature-dependent diffusivities of these three nuclides were then determined simultaneously by high precision stepped-heating and noble gas mass spectrometry. The outward mobility of proton-induced nuclides reflects diffusion through the quartz lattice. In the studied range of 70 to 400°C the helium diffusion coefficients exceed those of neon by 5-7 orders of magnitude. The implied diffusion parameters E_a = 153.7 ± 1.5 (kJ/mol) and ln(D_o/a²) = 15.9 ± 0.3 (ln(s⁻¹)) and E_a = 84.5 ± 1.2 (kJ/mol) and ln(D_o/a²) = 11.1 ± 0.3 (ln(s⁻¹)) for proton-induced ²¹Ne and ³He, respectively, indicate that cosmogenic neon will be quantitatively retained in inclusion-free quartz at typical Earth surface temperatures whereas cosmogenic helium will not. However, the neon diffusion parameters also indicate that diffusive loss needs to be considered for small (<1 mm) quartz grains that have experienced elevated temperatures. Since natural quartz often contains fluid inclusions which may enhance noble gas retentivity, these parameters likely represent an end-member case of purely solid-state diffusion. The ∼70 kJ/mol higher activation energy for neon diffusion compared to helium diffusion likely represents an energy barrier related to its ∼13% greater diameter and provides a fundamental constraint with which to test theories of solid state diffusion. The diffusion parameters for proton-induced ⁴He are indistinguishable from those for ³He, providing no evidence for the commonly expected inverse square root of the mass diffusion relationship between isotopes. We also find preliminary indication that increased exposure to radiation may enhance neon and helium retentivity in quartz at low temperatures.     

The Helium Isotopic Chemistry of Lake Bonney, Taylor Valley, Antarctica: Timing of Late Holocene Climate Change in Antarctica

To better understand the long-term climate history of Antarctica, we studied Lake Bonney in Taylor Valley, Southern Victoria Land (78°S). Helium isotope ratios and He, Ne, Ar and N₂ concentration data, obtained from hydrocasts in the East (ELB) and West (WLB) Lobes of Lake Bonney, provided important constraints on the lakes Holocene evolution. Based on very low concentrations of Ar and N₂ in the ELB bottom waters, ELB was free of ice until 200 ± 50 years ago. After which, low salinity water flowing over the sill from WLB to ELB, covered ELB and formed a perennial ice cover, inhibiting the exchange of gases with the atmosphere. In contrast to the ELB, the WLB retained an ice cover through the Holocene. The brine in the WLB bottom waters has meteoric N₂ and Ar gas concentrations indicating that it has not been significantly modified by atmospheric exchange or ice formation. The helium concentrations in the deep water of WLB are the highest measured in non-thermal surface water. By fitting a diffusional loss to the ³He/⁴He, helium, and Cl profiles, we calculate a time of 3000 years for the initiation of flow over the sill separating the East and West Lobes. To supply this flux of helium to the lake, a helium-rich sediment beneath the lake must be providing the helium by diffusion. If at any time during the last million years the ice cover left WLB, there would be insufficient helium available to provide the current flux to WLB. The variations in water levels in Lake Bonney can be related to climatic events that have been documented within the Southern Victoria Land region and indicate that the lakes respond significantly to regional and, perhaps, global climate forcing.     

Helium and argon isotopic compositions of the Longquanzhan gold deposit in the Yishu fault zone and their geological implications

The Longquanzhan gold deposit hosted in granitic cataclasites with mylontization of the foot wall of the main Yishui-Tangtou fault. 3He/4He ratios in fluid inclusions range from 0. 14 to 0. 24 R/Ra,close to those of the crust-source helium. 40Ar/36Ar ratios were measured to be 289-1811, slightly higher than those of atmospheric argon. The results of analysis of helium and argon isotopes suggested that ore-forming fluids were derived chiefly from the crust. The δ18O values of fluid inclusions from vein quartz range from -1.78‰ to 4.07‰, and the δD values of the fluid inclusions vary between -74‰ and -77‰. The hydrogen and oxygen isotope data indicated that the ore-forming fluid for the Longquanzhan gold deposit had mixed with meteoric water in the process of mineralization. This is consistent with the conclusion from the helium and argon isotope data.     

Source and movement of helium in the eastern Morongo groundwater Basin: The influence of regional tectonics on crustal and mantle helium fluxes

We assess the role of fracturing and seismicity on fluid-driven mass transport of helium using groundwaters from the eastern Morongo Basin (EMB), California, USA. The EMB, located ∼200 km east of Los Angeles, lies within a tectonically active region known as the Eastern California Shear Zone that exhibits both strike-slip and extensional deformation. Helium concentrations from 27 groundwaters range from 0.97 to 253.7 × 10⁻⁷ cm³ STP g⁻¹H₂O, with corresponding ³He/⁴He ratios falling between 1.0 and 0.26 R_A (where R_A is the ³He/⁴He ratio of air). All groundwaters had helium isotope ratios significantly higher than the crustal production value of ∼0.02 R_A. Dissolved helium concentrations were resolved into components associated with solubility equilibration, air entrainment, in situ production within the aquifer, and extraneous fluxes (both crustal and mantle derived). All samples contained a mantle helium-3 (³He_m) flux in the range of 4.5 to 1351 × 10⁻¹⁴ cm³ STP ³He cm⁻² yr⁻¹ and a crustal flux (J₀) between 0.03 and 300 × 10⁻⁷ cm³ STP ⁴He cm⁻² yr⁻¹. Groundwaters from the eastern part of the basin contained significantly higher ³He_m and deep crustal helium-4 (⁴He_dc) concentrations than other areas, suggesting a localized source for these components. ⁴He_dc and ³He_m are strongly correlated, and are associated with faults in the basin. A shallow thermal anomaly in a >3,000 m deep graben in the eastern basin suggests upflow of fluids through active faults associated with extensional tectonics. Regional tectonics appears to drive large scale crustal fluid transport, whereas episodic hydrofracturing provides an effective mechanism for mantle-crust volatile transport identified by variability in the magnitude of degassing fluxes (³He_m and J₀) across the basin.     

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.     

He,Ne, Ar,and C isotope systematics of geothermal emanations in the Lesser Antilles Islands Arc

We present He, Ne, Ar, and C isotope analyses of hydrothermal brines and gases from fumaroles, hot springs, mofettes and hydrothermal exploration drillings on the major islands of the Lesser Antilles Arc. The origin of hydrothermal brines, which have been analyzed also for O and H isotopes, is essentially meteoric-hydrothermal. Air-corrected isotope compositions of helium (2.2 Rc/Ra < ³He/⁴He < 8.6 Rc/Ra) and carbon (−20 < δ¹³C_PDB < +0.5) are variable and require a variety of crustal and magmatic sources. The diversity of δ¹³C_PDB and ³He/CO₂ ratios within individual volcanic centres suggests that crustal sources (e.g., limestone) contaminate magmatic CO₂ en route from high-level magma reservoirs (depth < 15 km) to the surface. A similar contamination may be found for magmatic helium on distal springs. The ³He/⁴He signature of summit fumaroles, thought to reflect the ³He/⁴He signature of high-level magmas, shows a remarkable systematic variation along the arc. In addition, there is a correlation throughout the arc between published Sr, Pb, and Nd isotope signatures of lavas and the ³He/⁴He signatures of summit fumaroles. On the northern islands (Nevis, Montserrat, Guadeloupe, and Dominica) summit fumaroles have the N-MORB signature (³He/⁴He = 8 ± 1 R/Ra), and the isotope signature of lavas is not dissimilar from comparable intra-oceanic arc tholeiites elsewhere. Variable enrichments in radiogenic Sr and Pb have been reported for lavas of individual volcanic centres of the Southern Islands (Martinique, St.Lucia, and Grenada), and summit fumaroles on these centres match these variations by variable radiogenic He-enrichments, i.e., lower ³He/⁴He ratios. This correlation suggests that radiogenic Sr and Pb enrichments of lavas and low ³He/⁴He signatures on summit fumaroles have a common origin, i.e., a terrigenous contaminant derived from the Orinoco depositionary fan. Crustal assimilation is thought to decouple the He isotope system from any other radiogenic isotope system and, therefore, we argue that the observed correlation of He, Sr, Pb, and Nd isotope systems is related to a terrigenous contaminant derived from subducted sediments. Support for this scenario also comes from the matching of low ³He/⁴He ratios and tectonic features of the forearc thought to favor the subduction of forearc sediments.The present study offers a first clue that, under suitable conditions, crustal helium from oceanic sediments might be subducted to the depth of arc magma sources and, possibly, even recycled into the deeper mantle.     

Helium measurements of pore fluids obtained from the San Andreas Fault Observatory at Depth (SAFOD, USA) drill cores

⁴He accumulated in fluids is a well established geochemical tracer used to study crustal fluid dynamics. Direct fluid samples are not always collectable; therefore, a method to extract rare gases from matrix fluids of whole rocks by diffusion has been adapted. Helium was measured on matrix fluids extracted from sandstones and mudstones recovered during the San Andreas Fault Observatory at Depth (SAFOD) drilling in California, USA. Samples were typically collected as subcores or from drillcore fragments. Helium concentration and isotope ratios were measured 4?C6 times on each sample, and indicate a bulk ⁴He diffusion coefficient of 3.5?±?1.3?×?10^?C8 cm²?s^?C1 at 21°C, compared to previously published diffusion coefficients of 1.2?×?10^?C18 cm²?s^?C1 (21°C) to 3.0?×?10^?C15 cm²?s^?C1 (150°C) in the sands and clays. Correcting the diffusion coefficient of ⁴He_water for matrix porosity (??3%) and tortuosity (??6?C13) produces effective diffusion coefficients of 1?×?10^?C8 cm^2?s^?C1 (21°C) and 1?×?10^?C7 (120°C), effectively isolating pore fluid ⁴He from the ⁴He contained in the rock matrix. Model calculations indicate that <6% of helium initially dissolved in pore fluids was lost during the sampling process. Complete and quantitative extraction of the pore fluids provide minimum in situ porosity values for sandstones 2.8?±?0.4% (SD, n?=?4) and mudstones 3.1?±?0.8% (SD, n?=?4).     

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.     

Diffusion of HTO,Cl and I in Upper Toarcian argillite samples from Tournemire: Effects of initial iodide concentration and ionic strength

Diffusion parameters for HTO, ³⁶Cl⁻_, and ¹²⁵I⁻ were determined on Upper Toarcian argillite samples from the Tournemire Underground Research Laboratory (Aveyron, France) using the through diffusion technique. The direction of diffusion was parallel to the bedding plane. The purpose of the present study was 3-fold; it was intended (i) to confirm the I⁻ interaction with Upper Toarcian argillite and to verify the effects of initial I⁻ concentration on this affinity, as previously observed by means of radial diffusion experiments, (ii) to highlight any discrepancy between Cl⁻ and I⁻ diffusivity, and (iii) to investigate the effect of an increase of the ionic strength of the solution on the anionic tracers’ diffusive behaviour. The results show that the effective diffusion coefficient (D_e) and diffusion accessible porosity (ε_a) values obtained with an ionic strength (I.S.) synthetic pore water of 0.01 eq L⁻¹ are: D_e = 2.35–2.50 × 10⁻¹¹ m² s⁻¹ and ε_a = 12.0–15.0% for HTO, and D_e = 14.5–15.5 × 10⁻¹³ m² s⁻¹ and ε_a = 2.5–2.9% for ³⁶Cl⁻. Because of anionic exclusion effects, anions diffuse slower and exhibit smaller diffusion accessible porosities than HTO, taken as a water tracer. The associated effective diffusion coefficient (D_e) and rock capacity factor (α) obtained for ¹²⁵I are: D_e = 7.00–8.60 × 10⁻¹³ m² s⁻¹ and α = 4.3–7.2%. Such values make it possible to calculate low ¹²⁵I distribution ratios (0.0057 < R_D < 0.0192 mL g⁻¹) which confirm the trend indicating that the ¹²⁵I rock capacity factor increases with the decrease of the initial I⁻ concentration. Additional through-diffusion experiments were carried out with a higher ionic strength synthetic pore water (I.S. = 0.11 eq L⁻¹). No evolution of HTO diffusion parameters was observed. The anionic tracers’ effective diffusion coefficient increased by a factor of two but no clear evolution of their accessible porosity was observed. Such a paradox could be related to the particularly small mean pore size of the Upper Toarcian argillite of Tournemire. The most significant finding of this study is the large discrepancy (factor of two) between the values of the effective diffusion coefficient for ¹²⁵I and ³⁶Cl. Whatever the ionic strength of the synthetic solution used, ¹²⁵I exhibited D_e values two times lower than those of ³⁶Cl. A detailed explanation for this difference cannot be given at present even if a hypothesis based on ion-pairing or on steric-exclusion cannot be excluded. This makes questionable the assumption usually made for quantifying ¹²⁵I sorption and postulating that ³⁶Cl and ¹²⁵I would diffuse in the same porosity. In other terms, at Tournemire, ¹²⁵I sorption could be more pronounced than previously indicated.     

Noble gas isotope sites and mobility in mafic rocks and olivine

Important He and Ar isotope studies on rocks and minerals, relevant to the geochemical and degassing history of the Earth, are often hampered by insufficient knowledge of the retentivity of different types of sites in minerals (inclusions, matrix) for these species, and of the relative importance of radiogenic and trapped components and possible differences in their behavior.To identify sites of noble gas isotopes, shed some light on their origin and estimate their residence times in olivine, which is a mineral considered as a good natural sampler, we investigated 2.5 Ga old ultramafic rocks from the Monche Pluton (Kola Peninsula, north-east part of the Baltic shield) using several extraction methods: crushing, fusion, slow step-wise and rapid incremental heating. Previous studies indicated that these rocks contain mainly trapped noble gases; however, to constrain the possible contribution of in-situ generated radiogenic helium, U and Th concentrations were also measured in the samples.The helium release pattern obtained by relatively fast (∼1.5 h long) incremental heating of olivine includes three distinct release peaks for helium: a low-temperature (600 °C) l-peak, a middle (800-1100 °C) m-peak and a high-temperature (∼1400 °C) h-peak. However, helium extraction from a powdered aliquot of the same olivine yields mainly the middle m-peak indicating that gases released in the l- and h-peaks occupy gas-liquid inclusions opened in the course of crushing and grinding. Moreover, slow step-wise heating (14 h) also results in a broad He release peak but in two well-separated l- and h-peaks of non-atmospheric ⁴⁰Ar∗. This feature implies helium migration from l- and h-vesicles into the matrix m during long step-wise heating experiments, whereas less movable Ar remains in inclusions at even relatively high almost-magmatic temperatures.Using a simple phenomenological model envisaging the three different residence sites for noble gases, both fast- and slow-heating release patterns for ⁴⁰Ar∗ and He, including those for the crushed sample, could be reproduced. The diffusion parameters inferred from the modeling of olivine (D₀ = 2.4 × 10⁻² cm² s⁻¹ and Ea = 133 kJ mol⁻¹) are similar to those published by Shuster et al. (2003) and Blard et al. (2008). The high matrix/fluid solubility coefficient for helium, H_He ∼ 0.01, exceeds estimates reported by Trull and Kurz (1993); however, the product D_He(T) × H_He, the “permeability” (that governs He migration in vesicles + matrix composed materials), is very similar to their value. Extrapolation to the ambient temperature (0 °C) gives long and similar helium residence times in l- and h-vesicles, exceeding 10¹⁰ yrs, and even longer time scales ∼10¹⁶ yrs are obtained for the helium residence in the matrix. Therefore, at low temperatures our samples may be considered as excellent samplers of trapped volatile species, including helium.     

Isotopic fractionation of noble gases by diffusion in liquid water: Molecular dynamics simulations and hydrologic applications

Despite their great importance in low-temperature geochemistry, diffusion coefficients of noble gas isotopes in liquid water (D) have been measured only for the major isotopes of helium, neon, krypton and xenon. Data on the diffusion coefficients of minor noble gas isotopes are essentially non-existent and so typically have been estimated by a kinetic-theory model in which D varies as the inverse square root of the isotopic mass (m): D ∝ m^−0.5. To examine the validity of the kinetic-theory model, we performed molecular dynamics (MD) simulations of the diffusion of noble gases in ambient liquid water. Our simulation results agree with available experimental data on the solvation structure and diffusion coefficients of the major noble gas isotopes and reveal for the first time that the isotopic mass-dependence of all noble gas self-diffusion coefficients has the power-law form D ∝ m^−β with 0 < β < 0.2. Thus our results call into serious question the widespread assumption that the ‘square-root’ model can be applied to estimate the kinetic fractionation of noble gas isotopes caused by diffusion in ambient liquid water. To illustrate the importance of this finding, we used the diffusion coefficients determined in our MD simulations to reconsider the geochemical modeling of ²⁰Ne/²²Ne and ³⁶Ar/⁴⁰Ar isotopic ratios in three representative hydrologic studies. Our new modeling results indicate that kinetic isotopic fractionation by diffusion may play a significant role in noble gas transport processes in groundwater.     

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.     

Noble gas and halogen evidence for the origin of Scandinavian sandstone-hosted Pb-Zn deposits

Fluid origins in the sandstone-hosted Pb-Zn class of ore deposit have been investigated in three deposits from Scandinavia; Laisvall, Vassbo and Osen. The deposits studied are hosted by autochthonous Cambrian sandstones that preserve a near original structural relationship to the underlying Precambrian basement, enabling the role of basement interaction to be assessed.Mineral samples have been collected from across the paragenetic sequence: sphalerite, galena, pyrite, fluorite and barite, of impregnation and related joint-hosted mineralization. Fluid-inclusion halogen (Cl, Br and I) and noble gas isotope (⁴⁰Ar, ³⁶Ar, ⁸⁴Kr) compositions were determined simultaneously by noble gas mass spectrometry of irradiated sample splits. Complementary He isotope analyses are obtained from nonirradiated splits of the same samples.³He/⁴He values at Laisvall and Osen are highly radiogenic, 0.02 Ra, and the ⁴He/⁴⁰Ar* ratio extends to values greater than the crustal production value of 5, characteristic of low-temperature crustal fluids. At Vassbo, a slightly elevated ³He/⁴He ratio of 0.1-0.3 Ra is compatible with a very minor mantle component (1%-4%) suggesting a distal source for the basinal brine-dominated fluid.Br/Cl molar ratios 3.2-8.2 × 10⁻³ are greater than the present seawater value of 1.54 × 10⁻³ and correspond with I/Cl molar ratios in the range 64-1600 × 10⁻⁶. The upper limits of both the I/Cl and Br/Cl values are amongst the highest measured in crustal fluids. Together, the data indicate acquisition of salinity by the evaporation of seawater beyond the point of halite saturation and subsequent fluid interaction with I-rich organic matter in the subsurface. The data are compatible with the independent transport of sulfate and sulfide and indicate that fluids responsible for joint-hosted mineralization were distinct to those responsible for impregnation mineralization.All three deposits preserve fluids with ⁴⁰Ar/³⁶Ar in the range of 6,000-10,000 and fluid inclusion ⁴⁰Ar* concentrations of >0.02-0.05 cm³cm⁻³. Fluid-inclusion ⁴He concentrations are also extremely elevated with maximum values of ∼0.1 cm³cm⁻³ in Laisvall fluorite and sphalerite. The high ⁴⁰Ar/³⁶Ar values, together with the high ⁴He and ⁴⁰Ar* concentrations, result from a very long premineralization crustal residence time on the order of 100-200 Ma.Together, the noble gas and halogen data are compatible with a Caledonian mineralization event (∼425 Ma) caused by mixing of two or more, long-lived, hydrothermal basinal brines and pore fluids at the sites of mineralization. The data suggest negligible recharge of the basinal brines by meteoric water and indicate extensive fluid-basement interaction before mineralization. The similar noble gas composition of each deposit, suggests that similar processes operated at all three deposits and favors a single-pass fluid-flow model for mineralization.     

Helium,Argon and Carbon Isotopic Compositions of Spring Gases in the Hainan Island,China

Chemical and isotopic compositions have been measured for N2-He-rich bubbling gases discharging from hot springs in the Hainan Island, Southern China. Observed 3He/4He ratios (0.1–1.3 RA) indicate the occurrence of a mantle component throughout the island, which has been highly diluted by a crustal radiogenic 4He component. The occurrence of mantle-derived helium is high in the northern island (12%–16% of total He) and gradually decreases towards southern coast (1%–3% of total He). Such a distribution pattern is most likely controlled by the Pleocene-Quaternary volcanic activities in the northern island and groundwater circulation along the deep major faults. The 40Ar/36Ar and N2/Ar ratios suggest that N2 and Ar of the hot spring gases are mostly meteoric. Although δ13C values of CO2 (–20‰ to –27‰) with low concentrations are consistent with the biogenic origin, the combination of 3He/4He and d13CCO2 suggests a two end-member mixing of mantle and crustal components with CO2/3He ratios of 2×109 and 8×1011, respectively. However, the low CO2/3He ratios (1–22×106) can not be ascribed in terms of the simple mixing but has to be explained by the addition of radiogenic 4He and loss of CO2 by calcite precipitation in the hydrothermal system, which is most likely controlled by the degree of gas-water-rock interaction.     

Activation energy for diffusion of helium in water-saturated, compacted Na-montmorillonite

It is important to clarify the migration behavior of hydrogen gas dissolved in water-saturated, compacted bentonite, which is a promising material for geologic disposal of high-level waste and TRU waste disposal. The diffusion coefficients of helium, which can be detected under extremely low background conditions, in water-saturated, compacted Na-montmorillonite were determined as a function of temperature by a transient diffusion method. The activation energies for diffusion of helium were then obtained. The activation energies were from 6.9 ± 4.8 to 19 ± 2.8 kJ mol^− 1 and were regarded to be independent of dry density. The activation energies of helium in water-saturated Na-montmorillonite were roughly equal to those in bulk water, 14.9 kJ mol^− 1, and in ice, from 11 to 13 kJ mol^− 1. It is possible that helium diffuses not only in pore water but also in interlayer water.     

Granite is an Effective Helium Source Rock: Insights from the Helium Generation and Release Characteristics in Granites from the North Qinling Orogen,China

Global helium(He) shortage is a challenging problem; however, the types of helium source rock and the mechanisms of He generation and release therein remain still poorly understood. In this study, in order to evaluate the potential of granite as an effective helium source rock, we collected granitic samples from the North Qinling Orogen, Central China, in the south of the helium-rich Weihe Basin. The helium generation and release behaviors in granite were studied through analysis of U and Th concentrations, EMPA images, and He and Ar concentrations and isotopic ratios extracted by crushing and stepwise heating. The results indicate that Ar has a better retention and a lower mobility than He. 3 He/4 He ratios released by crushing and stepwise heating are 0.016–0.056 RA and 0.003–0.572 RA, respectively, where RA is the atmospheric 3 He/4 He of 1.4×10-6, reflecting a crustal and radiogenic source. Helium concentrations extracted by the two ways are 0.13–0.95 ucm3 STP/g and 7.82–115.62 ucm3 STP/g, respectively, suggesting that matrix-sited He accounts for more than 98% of total helium preserved in granite. In addition, the total generated He amounts in granites are calculated based on the measured U and Th concentrations in granitic samples. Dividing the preserved He quantities by the generated He amounts, it turned out that less than 10% of He produced since the formation of the granite is preserved in the rock over geological time, suggesting that more than 90% generated He can be transferred to the Weihe Basin. Temperature and fracture are the two critical factors controlling He release. Based on the relationship between He diffusivity of granites and temperature and the He closure temperatures of a variety of U-and Th-rich minerals(27–250°C), we estimate that He can be partially released out of granite at the depths 400 m and totally released at the depths 7800 m. Fractures provide effective transfer of free He from deep source rocks to shallow reservoirs. Finally, a model on granite as an effective helium source rock is established. We suggest exploring He resources in hydrocarbon basins with granitic basement(or adjacent to granite bodies), high geothermal field, and young active fractures.     

^3He／^4He Ratios and Heat Flow in the Continental Rift—valley,Eastern China

Heat flow and the origin of helium in natural gases from fault basins of the continental rift-valley in eastern China are discussed in terms of helium isotope geochemistry.³He/⁴He ratios in natural gases from the rift-valley range from 2.23 × 10⁻⁷ to 7.21 × 10⁻⁶, which are directly proportional to the concentration of helium and ΣNHC/ΣHC ratio in natural gases. Geological and isotope geochemical data suggest that helium in natural gases consists predominantly of crustal radio-genic and upper mantle-derived helium. In a simple mixing pattern between crustal He and mantle-derived He, mantle-derived helium in natural gases would account for 10–60%. Calculated values for heat flow (Q) range from 59.7 to 82.4mWm⁻², of which about 60 percent in the rift-valley is derived from the upper mantle. Natural helium reservoirs would be found in the areas where the upper mantle uplifted greatly and heat flow is large in the continental rift-valley. The project is financially supported by the National Natural Science Foundation of China.     

Dating ultra-deep mine waters with noble gases and Cl, Witwatersrand Basin, South Africa

Concentrations and isotopic ratios of dissolved noble gases, ³⁶Cl, δD and δ¹⁸O in water samples from the ultra-deep gold mines (0.718 to 3.3 km below the surface) in the Witwatersrand Basin, South Africa, were investigated to quantify the dynamics of these ultra deep crustal fluids. The mining activity has a significant impact on the concentrations of dissolved gases, as the associated pressure release causes the degassing of the fissure water. The observed under saturation of the atmospheric noble gases in the fissure water samples (70-98%, normalized to ASW at 20°C and 1013 mbar) is reproduced by a model that considers diffusive degassing and solubility equilibration with a gas phase at sampling temperature. Corrections for degassing result in ⁴He concentrations as high as 1.55 · 10⁻¹cm³STP⁴He g⁻¹, ⁴⁰Ar/³⁶Ar ranging between 806 and 10331, and ¹³⁴Xe/¹³²Xe and ¹³⁶Xe/¹³²Xe ratios above 0.46 and 0.44, respectively. Corrected ^134(136)Xe/¹³²Xe and ^134(136)Xe/⁴He-ratios are consistent with their production ratios, whereas the nucleogenic ⁴He/⁴⁰Ar, and ^134(136)Xe/⁴⁰Ar ratios generally indicate that these gases are produced in an environment with an average [U + Th]/K-content 2-3 times above that of crustal average. In two scenarios, one considering only accumulation of in situ produced noble gases, the other additionally crustal flux components, the model ages for 14 individual water samples range from 13 to 168 Ma and from 1 to 23 Ma, respectively.The low ³⁶Cl-ratios of (4-37) · 10⁻¹⁵ and comparatively high ³⁶Cl-concentrations of (8-350) · 10⁻¹⁵ atoms ³⁶Cl l⁻¹ reflect subsurface production in secular equilibrium indicating an age in excess of 1.5 Ma or 5 times the half-life of ³⁶Cl.In combination, the results suggest residence times of the fluids in fissures in this region (up to 3.3 km depth) are of the order of 1-100 Ma. We cannot exclude the possibility of mixing and that small quantities of younger water have been mixed with the very old bulk.