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).     

Identification of He sources and estimation of He ages in groundwater of the North China Plain

Dissolved helium concentrations and ³He/⁴He ratios were measured for 18 groundwater samples collected from the Quaternary confined aquifers in the North China Plain (NCP). The dissolved helium concentrations ranged from 1 × 10⁻⁷ to 1 × 10⁻⁶ cm³STP·g⁻¹ in the 14 samples from the central plain, but was approximately two orders of magnitude higher, between 6 × 10⁻⁶ and 9 × 10⁻⁵ cm³STP·g⁻¹, in 4 samples from the coastal plain. Based on these concentrations and the corresponding ³He/⁴He ratios varying from 0.09 to 0.55 R_a (where R_a is the ³He/⁴He ratio of air), the dissolved helium in groundwater in the central plain was identified to be primarily a mixture of atmospheric helium with radiogenic helium and a representative radiogenic helium ratio was estimated to be 0.035 R_a. Despite the high fraction of terrigenic ⁴He in the samples from the coastal plain, their ³He/⁴He ratios were found to be significantly above this radiogenic value, ranging between 0.20 and 0.37 R_a, indicating the presence of a mantle-derived He component in this area. About 2–4% mantle helium was estimated to be present in the groundwater of the coastal plain, which probably is associated with the regional Cangdong fault and tectonic activities. Based on the radiogenic He component, ⁴He ages of the groundwater in the central plain were calculated by assuming either pure in situ production or an external helium flux J₀ of 4.7 × 10⁻⁸ cm³STPcm⁻²a⁻¹. The estimated ⁴He ages fall between 9.5 and 51.4 ka and are comparable to the ¹⁴C ages, suggesting that the results of ⁴He dating are reasonable and can be an effective tool to estimate groundwater residence times under suitable conditions.     

A New 190Pt-4He method of native platinum age determination

A new method of determining the age of native platinum based on alpha-radioactivity of one of its natural isotopes ¹⁹⁰Pt is proposed. Due to a special form of occurrence of radiogenic helium in the crystal lattice of native metals as a helium cluster-bubbles, the stability of ¹⁹⁰Pt-⁴He of the isotope system is extremely high in the natural environment. To check the efficiency of the proposed ¹⁹⁰Pt-⁴He method of isotope geochronology, six independent mineral aggregates of native platinum from chromite-bearing dunites of the southern part of platinum-bearing zonal Galmoenan dunite-cllinopyroxenite-gabbro plutonic complex (Koryak-Kamchatka belt, Russia) were analyzed. The age calculated by the tangent of the ¹⁹⁰Pt-⁴He isochrone slope angle equals 69.5 ± 4.9 mln years. The obtained age value coincides with the results of isotope datings, which were made previously by different methods of isotope geochronology.     

Helium isotopes on the Macdonald seamount (Austral chain): constraints on the origin of the superswell

We present new helium isotope data from the Macdonald seamount (Austral chain). The helium isotopic ratio varies from ⁴He/³He=45 000 (R/Ra=16.0) to 200 170 (R/Ra=3.6). The helium content is between 1.5×10^?8 and 1.1×10^?5 ccSTP/g. These helium results show clearly the presence of primitive mantle material in the source of the Austral chain. Macdonald has the lowest ⁴He/³He ratio among the Polynesian submarine volcanoes, except Hawaii (Loihi). The simplest explanation for the primitive helium signature is the presence under Macdonald of a mantle plume that derives either from the 670 km or 2900 km boundary layers, or, eventually, from the top of a large mantle dome resulting from a stratified two-layer convection. This plume contains less-degassed material with low ⁴He/³He ratio. To cite this article: M. Moreira, C. Allègre, C. R. Geoscience 336 (2004).     

Helium and neon isotope geochemistry of some ground waters from the Canadian Precambrian Shield

Ground waters in a Precambrian granitic batholith at the Whiteshell Nuclear Research Establishment (WNRE) in Pinawa, Manitoba contain between 5 × 10^?5 and 10^?1 cc STP/g_H2O of radiogenic helium-4 but have relatively uniform ³He/⁴He ratios of between 0.6 × 10^?8 and 2.3 × 10³. The highest helium samples also contain radiogenic ^21,22Ne produced by (α,n) or (n,α) reactions with other isotopes. As much as 1.8 × 10^?9ccSTP/g_H2O of excess ²¹Ne and 3.8 × 10^?9ccSTP/gH₂O of excess ²²Ne have been measured. Helium and ²¹Ne ages of these ground waters, calculated on the basis of known crustal production rates of ⁴He and ²¹Ne, are unreasonably high (up to 2 × 10⁵ years) and incompatible with the ¹⁴C ages and other isotopic and hydrogeologic data. Uranium enrichment in the flow porosity of the granite may dominate ⁴He and ^21,22Ne production in this granite and mask the contributions from more typical U and Th concentrations in the rock matrix.At the Chalk River Nuclear Laboratories in Ontario helium concentrations in ground waters in a Precambrian monzonitic gneiss range from 1.5 × 10^?7 to 8.7 × 10^?4ccSTP/g_H2O with the ³He/⁴He ratios ranging from 2.0 × 10^?3 to 1.5 × 10^?7. The highest helium concentrations may be attributable to the presence of a thick uraniferous pegmatite vein and yield helium ages more than two orders of magnitude higher than the ¹⁴C ages. Application of He age dating equations to ground waters from Precambrian granitic rocks requires knowledge of the nature of uranium and thorium enrichment in the subsurface in order to select appropriate values for porosity and uranium and thorium concentration in the rock.     

New geochronometer for the direct isotopic dating of native platinum minerals (190Pt-4He method)

A new method of isotope geochronology was proposed for dating native platinum minerals on the basis of the ??-decay of the natural isotope ¹⁹⁰Pt. The analysis of the thermal desorption of helium in the crystal lattice of native metals, including platinum, allowed us to predict a very high thermal stability (retentivity) of radiogenic ⁴He in native platinum minerals up to their melting temperatures. In order to validate the proposed ¹⁹⁰Pt-⁴He method, direct isotopic dating was performed for isoferroplatinum from the Galmoenan dunite-clinopyroxenite and Kondyor alkaline ultramafic massifs. The results of dating obtained by this method for primary ore platinum from the Galmoenan Massif (70 ± 5 Ma) are consistent with geological observations and mean Sm-Nd and Rb-Sr isotopic age estimates. The ¹⁹⁰Pt-⁴He age obtained for placer isoferroplatinum from the Kondyor Massif (112 ± 7 Ma) also agrees with geological observations and is close to the K-Ar and Rb-Sr ages of koswites (phlogopite-magnetite pyroxenites, gabbros, nepheline syenites, and metasomatic rocks after dunites). Our experimental data demonstrated that the ¹⁹⁰Pt-⁴He method is a promising tool for dating native platinum minerals.     

Geothermochronology based on noble gases: III. Migration of radiogenic He in the crystal structure of native metals with applications to their isotopic dating

It was shown that the behavior of ⁴He in native and technical metals is very similar owing to the symmetric and stable electron shells of its atoms, which cannot gain electrons from other atoms or donate their own electrons to metal atoms in a crystal lattice. Therefore, they rapidly migrate toward grain boundaries and dislocations, where they are released as vesicles or He clusters. It was found that the thermal desorption of radiogenic He occurring in the crystal lattice of native metals as gas clusters requires activation energies of 100 and even 180 kcal/mol up to the attainment of the melting temperature of the metal. The frequency factor is several orders of magnitude higher than the limiting value k ₀ ∼ 10¹³ s⁻¹ for the migration of single atoms in the crystal lattice. Near the melting temperature and tens-hundreds degrees above it, the character of the thermal desorption of radiogenic ⁴He changes fundamentally. The migration is strongly accelerated, and sharp narrow peaks appear on the kinetic curves of thermal desorption. A similar phenomenon was observed during the annealing of technical metals and is known as the burst-effect. The destruction of the crystal structure results in the disappearance of helium clusters (vesicles). At the very high temperature, He migrates as individual atoms relatively rapidly from the melt. The activation energy for He thermal desorption and the pre-exponential frequency factor acquire values characteristic of ordinary migration. Such peculiarities of radiogenic He provide unique opportunities for its preservation in the structure of gold and other native metals below their melting temperatures. The rapid advances of (U-Th)/He geochronology is still hampered by the experimentally established extremely heterogeneous distribution of U, He, and, probably, Th in the structure of gold and other natural metals. This difficulty can be circumvented by the development of a method for the determination of the contents of all the mentioned chemical elements in a single aliquot from each sample.     

Age and metal source of orogenic gold deposits in Southeast Guizhou Province,China: Constraints from Re-Os and He-Ar isotopic evidence

The orogenic gold deposits in Southeast Guizhou are an important component of the Xuefeng polymetallic ore belt and have significant exploration potential, but geochronology research on these gold deposits is scarce. Therefore, the ore genetic models are poorly constrained and remain unclear. In the present study, two important deposits(Pingqiu and Jinjing) are investigated, including combined Re-Os dating and the He-Ar isotope study of auriferous arsenopyrites. It is found that the arsenopyrites from the Pingqiu gold deposit yielded an isochron age of 400 ± 24 Ma,with an initial ~(187)Os/~(188)Os ratio of 1.24 ± 0.57(MSWD = 0.96). An identical isochron age of 400 ± 11 Ma with an initial ~(187)Os/~(188)Os ratio of 1.55 ± 0.14(MSWD = 0.34) was obtained from the Jinjing deposit. These ages correspond to the regional Caledonian orogeny and are interpreted to represent the age of the main stage ore. Both initial ~(187)Os ratios suggest that the Os was derived from crustal rocks. Combined with previous rare earth element(REE), trace elements, Nd-Sr-S-Pb isotope studies on scheelite, inclusion fluids with other residues of gangue quartz, and sulfides from other gold deposits in the region, it is suggested that the ore metals from Pingqiu and Jinjing were sourced from the Xiajiang Group. The He and Ar isotopes of arsenopyrites are characterized by ~3 He/~4 He ratios ranging from 5.3 × 10~(-4) Ra to 2.5 × 10~(-2) Ra(Ra = 1.4 × 10~(-6), the ~3 He/~4 He ratio of air), 40 Ar=/~4 He ratios from 0.64 × 10~(-2) to 15.39×10~(-2), and ~(40)Ar/~(36)Ar ratios from 633.2 to 6582.0. Those noble gas isotopic compositions of fluid inclusions also support a crustal source origin,evidenced by the Os isotope. Meanwhile, recent noble gas studies suggest that the amount of in situ radiogenic ~4 He generated should not be ignored, even when Th and U are present at levels of only a few ppm in host minerals.     

Spatial variations in 3He/4He ratios along a high strain rate zone,central Japan

A linear zone with high strain rates along the Japan Sea coast, the Niigata-Kobe Tectonic Zone (NKTZ), is considered to be associated with rheological heterogeneities in the lower crust and/or upper mantle. Helium isotope variations along the NKTZ reveal a close association with the geophysical evidence for rheological heterogeneities in the crust and mantle. In the southern NKTZ, the ³He/⁴He ratios lower than 3.4 Ra (Ra denotes the atmospheric ³He/⁴He ratio of 1.4 × 10⁻⁶) could be interpreted as a two-component mixture of helium stored in aqueous fluids driven off the subducting oceanic crust and radiogenic crustal helium. Higher ³He/⁴He ratios are observed in the central NKTZ where Quaternary volcanoes and high-temperature hot springs are concentrated, suggesting that the ³He emanation manifest in the central NKTZ results from the effective transfer of mantle helium by intrusion and degassing of mantle-derived magma in the crust. In the northern NKTZ where two large inland earthquakes occurred recently, there appears to be many samples with ³He/⁴He ratios significantly higher than those observed in the fore-arc side of northeast Japan. A plausible source of mantle helium could be attributed to upward mobilization of aqueous fluids generated by dehydration of the subducting Pacific Plate slab.     

河南桐柏老湾金矿床氢氧氦同位素地球化学及成矿流体来源

河南桐柏老湾金矿床的成矿作用是在变基性火山碎屑沉积岩为矿源层的背景上演化的。本文根据矿床氢氧同位素研究,认为矿床的热液成矿期成矿流体为大气降水和老湾花岗岩岩浆水的混合,成矿Ⅰ阶段和Ⅱ阶段以岩浆水为主,成矿Ⅲ阶段以大气降水为主,但在成矿Ⅱ阶段大气降水已占有很大的比例。氦同位素分析表明,在老湾金矿形成过程中有地幔流体加入,且从成矿Ⅱ阶段至Ⅲ阶段,由于大气降水比例增大,其与地幔流体的混合导致成矿流体的³He/⁴He比值不断减小。     

4He diffusion in specular hematite

In order to test the chronometer qualities of speculante for the (U + Th)/He dating method, ⁴He release experiments by stepwise heating of two specularites from the Rimbach mineralization locality in the southern Vosgues (France) have been carried out. The diffusion coefficients define linear Arrhenius plots within a temperature interval of 250 to 830 °C, which is suggestive of volume diffusion. Extrapolation of the diffusion behavior to 20° C yields diffusion coefficients (D₂₀ values) smaller than 10^?26 [cm² s^?1] for both hematites with activation energies at 116 [kJ/mole]. The results of our study suggest that specularite is a very helium retentive hematite variety which is capable of quantitatively retaining radiogenic helium over geologic periods of time.     

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.     

Stable isotope geochemistry and Re–Os ages of the Yinan gold deposit,Shandong Province,northeastern China

The Yinan gold deposit in the Luxi area of Shandong Province in northeastern China is a skarn-type ore deposit. In this article, we present results from sulphur, lead, carbon–oxygen, and helium–argon isotope chemistry to characterize the ore genesis and source features. We also present rhenium–osmium ages from molybdenite to evaluate the timing of ore formation. The δ³⁴S values of pyrite from the ore deposit range from 0.7‰ to 5.60‰ with a mean at 2.70‰, close to mantle and meteorite sulphur. Among Pb isotopes, ²⁰⁶Pb/²⁰⁴Pb values range from 18.375 to 18.436, ²⁰⁷Pb/²⁰⁴Pb values from 15.694 to 15.8, and ²⁰⁸Pb/²⁰⁴Pb values from 38.747 to 39.067. The δ¹³C values of calcite associated with the ores range from ?0.2‰ to ?0.5‰ and their δ¹⁸O values show variation from 9.4‰ to 12.6‰, suggesting a mixed fluid source. The ³He/⁴He and ⁴⁰Ar/³⁶Ar ratios of fluids trapped in pyrite are in the range of 0.27–1.11 Ra and 439.4–826, respectively, with calculated proportion of the mantle-derived He ranging from 3.25% to 14.03% and atmosphere argon ranging from 35.8% to 67.3%. The data suggest that the ore-forming fluids were derived from the crust and were mixed with a distinct contribution of mantle helium. The Re and Os values vary from 32 × 10^?6 to 93.02 × 10^?6 and from 0.01 × 10^?9 to 0.34 × 10^?9, respectively. The model ages of molybdenite range from 126.96 ± 1.82 Ma to 129.49 ± 2.04 Ma, with a weighted mean age of 128.08 ± 0.75 Ma and isochron age of 130.3 ± 3 Ma. These ages are close to the age of the associated quartz diorite porphyrite pluton, suggesting a close relationship between Cretaceous magmatism and metallogeny in NE China. A comparison of the Yinan gold deposit in the Luxi area with those of the Jiaodong area shows that the contrast in metallogenic features between the two are linked with the tectonic and geodynamic history.     

A New Single Vacuum Furnace Design for Cosmogenic 3He Dating

Helium‐3 is a stable cosmogenic isotope that can be used to determine the time interval during which a rock sample has been at or close to the Earth’s surface. As a result of the high production rate of ‘cosmogenic’³He (≈ 130 at g^?1 year^?1) and the low detection limit of modern mass spectrometers, it is possible to date exceptionally young surfaces (≈ 1000 years). The precision and accuracy of cosmogenic ³He measurements depend critically on the passive helium blank (produced by the metalwork of the extraction furnace) which can be significant relative to the sample signals. We have developed and constructed, at the CRPG (Nancy, France), a new high temperature furnace (< 1500 °C) to extract helium in minerals such as apatite, pyroxene and olivine at 1050, 1350 and 1450 °C, respectively. The furnace demonstrated an excellent helium extraction yield (> 99% for olivine and pyroxene for heating times of 20–30 min and temperatures in the range 1050–1450 °C) and low residual helium contributions (the blank, obtained under the same analytical conditions as for sample extraction: 1 × 10^?15 mole ⁴He and < 4 × 10^?21 mole ³He). This is approximately an order of magnitude lower than those reported by other laboratories using conventional furnaces.     

^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.     

内蒙古哈达门沟金矿成矿流体来源的氦、氩同位素示踪

内蒙古包头市哈达门沟金矿床是华北陆块北缘乌拉山-大青山地区的大型金矿床,矿床赋存于新太古界乌拉山群黑云角闪斜长片麻岩、角闪黑云二长片麻岩和含石榴石黑云斜长片麻岩中,成矿流体性质不明。文章对哈达门沟金矿主要载金矿物黄铁矿开展了流体包裹体中的He、Ar同位素组成研究。研究表明,赋存于黄铁矿流体包裹体中的4He含量为(83.92~606.46)×10-8cm3STP/g,n(3He)/n(4He)值为0.19~0.91Ra,幔源He的含量为2.62%~13.73%,平均为9.95%,表明成矿流体中的He主要来源于地壳,大约10%来源于地幔。~(40)Ar含量为(71.22~308.22)×10~(-8)cm~3STP/g,~(40)Ar/~(36)Ar比值变化于2793.6~7253.5之间,在n(~(40)Ar)/n(~(36)Ar)与R/Ra图解和n(~(40)Ar*)/n(4He)与R/Ra图解中,显示地壳氩和地幔氩的混合来源特征。结合已有的氢、氧、硫同位素研究,认为哈达门沟金矿成矿流体主体为地壳来源,但幔源流体的加入清晰可辨,乌拉特前旗-呼和浩特山前断裂很可能为富钾质壳幔混合流体的运移提供了通道和动力。     

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.     

Stable isotopes and noble gases in the Xishimen gold deposit,central North China Craton: metallogeny associated with lithospheric thinning and crust–mantle interaction

Quartz-vein type gold mineralization at Xishimen is a recently discovered gold deposit in the central North China Craton. More than 50 auriferous quartz veins occur in this region within a NNW–SSE-trending fault zone 4600 m in length and 3–10 m wide. Wall rocks are mainly Precambrian tonalite–trondhjemite–granodiorite (TTG) gneisses and associated supracrustals, modified by K-feldspathization and pyrite-phyllic hydrothermal alteration. Based on detailed field and petrographic studies, we identify five episodes of mineralization: pyrite-phyllic stage (I), coarse-grained pyrite-milky white quartz stage (II), fine-grained smoky grey quartz-pyrite stage (III), fine-grained smoky grey quartz-polymetallic sulphide stage (IV), and quartz-carbonate stage (V). We present results of δ³⁴S analysis of sulphide minerals from the different stages which show tightly clustered values in the range of –1.0‰ to 2.1‰, close to those of mantle and meteorite sulphur. Lead isotopic ratios of pyrite from the early to main stages also show restricted ranges with ²⁰⁶Pb/²⁰⁴Pb of 16.289–17.286, ²⁰⁷Pb/²⁰⁴Pb of 15.217–15.453, ²⁰⁸Pb/²⁰⁴Pb of 37.012–38.232, implying lower crustal input. ³He/⁴He and ⁴⁰Ar/³⁶Ar ratios of fluid trapped in pyrite are 0.68 Ra to 1.20 Ra (where Ra is the ³He/⁴He ratio of air = 1.4 × 10^?6) and 540.9–1065, respectively. ³He and ⁴Ar concentrations vary from 10.05 to 18.5 (10^?7 cm³STP/g) and 6.15 to 17.4 (10^?7cm³STP/g), respectively, with calculated mantle helium ranging from 8.47% to 14.96% (average 11.01%). δ¹⁸O_Q and δ¹⁸D_Q values of quartz range from 8.0‰ to 13.2‰ and –101.9‰ to –70.5‰, respectively, with calculated δ¹⁸O_W values of the mineralizing fluid ranging from 1.11‰ to 5.72‰, suggesting the mixing of magmatic aqueous fluid with meteoric water during gold precipitation. We correlate the mixed crust–mantle signature of the ore-forming sources to magmatism and metallogeny associated with Mesozoic inhomogeneous lithosphere thinning in the central North China Craton.     

Weathering geochronology by (U-Th)/He dating of goethite

Nine samples of supergene goethite (FeOOH) from Brazil and Australia were selected to test the suitability of this mineral for (U-Th)/He dating. Measured He ages ranged from 61 to 8 Ma and were reproducible to better than a few percent despite very large variations in [U] and [Th]. In all samples with internal stratigraphy or independent age constraints, the He ages corroborated the expected relationships. These data demonstrate that internally consistent He ages can be obtained on goethite, but do not prove quantitative ⁴He retention. To assess possible diffusive He loss, stepped-heating experiments were performed on two goethite samples that were subjected to proton irradiation to produce a homogeneous distribution of spallogenic ³He. The ³He release pattern indicates the presence of at least two diffusion domains, one with high helium retentivity and the other with very low retentivity at Earth surface conditions. The low retentivity domain, which accounts for ∼ 5% of ³He, contains no natural ⁴He and may represent poorly crystalline or intergranular material which has lost all radiogenic ⁴He by diffusion in nature. Diffusive loss of ³He from the high retentivity domain is independent of the macroscopic dimensions of the analyzed polycrystalline aggregate, so probably represents diffusion from individual micrometer-size goethite crystals. The ⁴He/³He evolution during the incremental heating experiments shows that the high retentivity domain has retained 90%-95% of its radiogenic helium. This degree of retentivity is in excellent agreement with that independently predicted from the helium diffusion coefficients extrapolated to Earth surface temperature and held for the appropriate duration. Considering both the high and low retentivity domains, these data indicate that one of the samples retained 90% of its radiogenic ⁴He over 47.5 Ma and the other retained 86% over 12.3 Ma. Thus while diffusive-loss corrections to supergene goethite He ages are required, these initial results indicate that the corrections are not extremely large and can be rigorously quantified using the proton-irradiation ⁴He/³He method.     

Changes in isotope ratio and content of dissolved helium through groundwater evolution

The dissolved He content and He isotope ratio are proxy indicators of groundwater evolution in the Shimokita peninsula. The record of ³H and excess bomb tritiogenic ³He reveals the intrusion depth of shallow and young groundwater into deep groundwater. The record of tritiogenic ³He suggests that prior to the period of nuclear testing, the natural production level of ³H irradiated by cosmic rays was probably 6 TU. Helium isotope ratios in the groundwater converge to that of the regional crustal He with increasing depth and dissolved He content. The regional degassed He has a ³He/⁴He (R) ratio of 7.24 × 10⁻⁷ which consists of 6% mantle He (with R=1. 1 × 10⁻⁵) and 94% radiogenic He (with R=1 ×10⁻⁸). The magnitude of degassing He flux is 5×10⁻⁹ m³/m² a. Based on the accumulation of He, and taking into consideration the degassing He flux, groundwater at depths greater than 300 m below sea level is estimated to be stagnant, exhibiting residence times in excess of 10² Ka.