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.     

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.     

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.     

Diffuse gas emissions at the Ukinrek Maars,Alaska: Implications for magmatic degassing and volcanic monitoring

Diffuse CO₂ efflux near the Ukinrek Maars, two small volcanic craters that formed in 1977 in a remote part of the Alaska Peninsula, was investigated using accumulation chamber measurements. High CO₂ efflux, in many places exceeding 1000 g m⁻² d⁻¹, was found in conspicuous zones of plant damage or kill that cover 30,000–50,000 m² in area. Total diffuse CO₂ emission was estimated at 21–44 t d⁻¹. Gas vents 3-km away at The Gas Rocks produce 0.5 t d⁻¹ of CO₂ that probably derives from the Ukinrek Maars basalt based on similar δ¹³C values (∼−6‰), ³He/⁴He ratios (5.9–7.2 R_A), and CO₂/³He ratios (1–2 × 10⁹) in the two areas. A lower ³He/⁴He ratio (2.7 R_A) and much higher CO₂/³He ratio (9 × 10¹⁰) in gas from the nearest arc-front volcanic center (Mount Peulik/Ugashik) provide a useful comparison. The large diffuse CO₂ emission at Ukinrek has important implications for magmatic degassing, subsurface gas transport, and local toxicity hazards. Gas–water–rock interactions play a major role in the location, magnitude and chemistry of the emissions.     

Constraints on the loss of matrix-sited helium during vacuum crushing of mafic phenocrysts

Vacuum crushing is an efficient technique to selectively release the mantle-derived helium component trapped within olivine and pyroxene phenocrysts. However, contrary to previous assumptions, recent studies have shown that this method may liberate significant matrix-sited cosmogenic ³He (³He_c) or radiogenic ⁴He (⁴He^∗). Because this loss may bias both the determination of magmatic ³He/⁴He ratios and the accuracy of ³He_c measurements, it is essential to understand what mechanism is responsible and under what conditions matrix helium loss is manifest. To address this question, olivines and pyroxenes with various amounts of matrix-sited ³He (from 10⁷ to 10¹¹ at. g⁻¹) were crushed in air or in vacuum using several crushing devices. Sample temperature was controlled during each crushing experiment, and ranged from 25 to 325 °C. The resulting powders were then sieved to obtain several homogeneous grain fractions ranging between <10 and >300 μm. The ³He_c concentrations measured in each fraction clearly show that significant ³He_c loss (>20%) affects only the finest fraction (<10 μm) and, importantly, only under hot conditions (here T ?300 °C). Even the smallest fractions (<10 μm) quantitatively retain matrix-sited ³He_c when crushed under cold conditions (T ?25 °C), regardless of the duration and energy of crushing. These results invalidate the model previously proposed by (Yokochi R., Marty B., Pik R. and Burnard P. (2005) High ³He/⁴He ratios in peridotite xenoliths from SW Japan revisited: evidence for cosmogenic ³He released by vacuum crushing. Geochem. Geophys. Geosyst.6, doi:10.1029/2004GC000836) that involved spallation tracks and implied that the magnitude of loss was mainly controlled by the grain size. Moreover, new diffusion experiments were carried out to constrain the diffusivity of matrix-sited helium in crushed olivines. When used to model diffusive ³He_c loss as a function of grain size during crushing, these new data predict the observed release fairly well. Therefore, we conclude that temperature-enhanced volume diffusion is one of the main mechanisms controlling the release of ³He_c during crushing. For future applications, special attention should thus be paid to control the grain size, the crushing duration, and the temperature of the sample.     

Noble gas composition of the solar wind as collected by the Genesis mission

We present the elemental and isotopic composition of noble gases in the bulk solar wind collected by the NASA Genesis sample return mission. He, Ne, and Ar were analyzed in diamond-like carbon on a silicon substrate (DOS) and ^84,86Kr and ^129,132Xe in silicon targets by UV laser ablation noble gas mass spectrometry. Solar wind noble gases are quantitatively retained in DOS and with exception of He also in Si as shown by a stepwise heating experiment on a flown DOS target and analyses on other bulk solar wind collector materials. Solar wind data presented here are absolutely calibrated and the error of the standard gas composition is included in stated uncertainties. The isotopic composition of the light noble gases in the bulk solar wind is as follows: ³He/⁴He: (4.64 ± 0.09) × 10⁻⁴, ²⁰Ne/²²Ne: 13.78 ± 0.03, ²¹Ne/²²Ne: 0.0329 ± 0.0001, ³⁶Ar/³⁸Ar 5.47 ± 0.01. The elemental composition is: ⁴He/²⁰Ne: 656 ± 5, and ²⁰Ne/³⁶Ar 42.1 ± 0.3. Genesis provided the first Kr and Xe data on the contemporary bulk solar wind. The preliminary isotope and elemental composition is: ⁸⁶Kr/⁸⁴Kr: 0.302 ± 0.003, ¹²⁹Xe/¹³²Xe: 1.05 ± 0.02, ³⁶Ar/⁸⁴Kr 2390 ± 150, and ⁸⁴Kr/¹³²Xe 9.5 ± 1.0. The ³He/⁴He and the ⁴He/²⁰Ne ratios in the Genesis DOS target are the highest solar wind values measured in exposed natural and artificial targets. The isotopic composition of the other noble gases and the Kr/Xe ratio obtained in this work agree with data from lunar samples containing “young” (∼100 Ma) solar wind, indicating that solar wind composition has not changed within at least the last 100 Ma. Genesis could provide in many cases more precise data on solar wind composition than any previous experiment. Because of the controlled exposure conditions, Genesis data are also less prone to unrecognized systematic errors than, e.g., lunar sample analyses. The solar wind is the most authentic sample of the solar composition of noble gases, however, the derivation of solar noble gas abundances and isotopic composition using solar wind data requires a better understanding of fractionation processes acting upon solar wind formation.     

He diffusion systematics in minerals: Evidence from synthetic monazite and zircon structure phosphates

Helium diffusivity was measured in synthetic rare-earth-element orthophosphates with systematically varying properties to evaluate potential controls on He transport in minerals. In the zircon structure phosphates (in this study, the phosphates of Tb, Dy, Ho, Er, Tm, Yb, and Lu as well as synthetic xenotime, YPO₄), He diffusion is strongly anisotropic. Transport apparently proceeds preferentially through channels aligned with the c-axis. The activation energy for diffusion is almost the same (122 ± 6 kJ/mol) in all members of this family, but there is a monotonic decrease in D_o with atomic number from TbPO₄ (∼10⁵ cm²/s) to LuPO₄ (∼10 cm²/s). The c-parallel channels become increasingly constricted in the same sequence, likely accounting for the systematically decreasing diffusivity. The He closure temperature (r = 1 cm, dT/dt = 10 °C/Myr) increases with atomic number from 44 °C for TbPO₄ to 88 °C for LuPO₄. Diffusion of radiogenic helium from natural zircon and xenotime is much slower than these synthetic analogs predict, suggesting that coupled substitution of REE and P for Zr and Si and/or radiation damage profoundly modify the energetics of interstitial He diffusion. In particular, α-recoil may play a key role by damaging the continuity and integrity of the channels.Monazite structure phosphates (here La, Ce, Pr, Nd, Sm, and Gd phosphate) are far more He retentive than those of the zircon structure. Activation energies increase smoothly with atomic number from LaPO₄ (183 kJ/mol) to NdPO₄ (224 kJ/mol) then decrease again to GdPO₄ (198 kJ/mol). D_o values mimic this pattern, spanning a range from ∼10⁻¹ cm²/s (GdPO₄) to 10⁴ cm²/s (NdPO₄). Nevertheless, He closure temperatures increase monotonically with atomic number, from 300 °C in LaPO₄ to 410 °C in GdPO₄. No evidence was obtained bearing on diffusion anisotropy, but the monazite structure lacks through-going channels so it is not expected. Diffusion parameters for radiogenic helium in natural monazite are similar to those obtained on the synthetic analogs.Ionic porosity is not the primary control on He diffusion in the orthophosphates. Within a given structure and with limited elemental substitution, ionic porosity and He closure temperature are negatively correlated, as predicted. However, differences between crystal structures are far more important than ion packing density: at comparable ionic porosity the monazite structure phosphates have He closure temperatures ∼300 °C higher than the xenotime structure phosphates. Modifications to the structures by radiation damage likely play a similarly significant role in controlling He diffusion.     

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

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

Laser depth profiling studies of helium diffusion in Durango fluorapatite

Ultraviolet lasers coupled with sensitive mass spectrometers provide a useful way to measure laboratory-induced noble gas diffusion profiles in minerals, thus enabling the calculation of diffusion parameters. We illustrate this laser ablation depth profiling (LADP) technique for a previously well-studied mineral-isotopic system: ⁴He in Durango fluorapatite. LADP studies were conducted on oriented, polished slabs from a single crystal that were heated under vacuum to a variety of temperatures between 300 and 450 °C for variable times. The resolved ⁴He profiles exhibited error-function loss as predicted by previous bulk ⁴He diffusion studies. All of the slabs, regardless of crystallographic orientation, yielded modeled diffusivities that are statistically co-linear on an Arrhenius diagram, suggesting no diffusional anisotropy of ⁴He in this material. The data indicate an activation energy of 142.2 ± 5.0 (2σ) kJ/mol and diffusivity at infinite temperature - reported as ln(D₀) - of −4.71 ± 0.94 (2σ) m²/s. These values imply a bulk closure temperature for ⁴He in Durango fluorapatite of 74 °C for a 50 μm radius grain, infinite cylinder geometry, and a cooling rate of 10 °C/Myr.     

Dynamics of the Galapagos hotspot from helium isotope geochemistry

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

Regional and temporal variations in CO2/He,He/He and δC along the North Anatolian Fault Zone,Turkey

New He and C relative abundance, isotope and concentration results from nine geothermal locations situated along an 800-km transect of the North Anatolian Fault Zone (NAFZ), Turkey, that were monitored during the period November 2001–November 2004, are reported. The geothermal waters were collected every 3–6 months to study possible links between temporal geochemical variations and seismic activity along the NAFZ. At the nine sample locations, the He isotope ratios range from 0.24 to 2.3R_A, δ¹³C values range from −4.5 to +5.8‰, and CO₂/³He ratios range from 5 × 10⁹ to 5 × 10¹⁴. The following geochemical observations are noted: (1) the highest ³He/⁴He ratios are found near the Galatean volcanic region, in the central section of the NAFZ, (2) at each of the nine sample locations, the ³He/⁴He ratios are generally constant; however, CO₂/³He ratios and He contents both show one order of magnitude variability, and δ¹³C values show up to ∼4‰ variability, and (3) at all locations (except Re?adiye), δ¹³C values show positive correlations with CO₂ contents. The results indicate that at least three processes are necessary to account for the geochemical variations: (1) binary mixing between crustal and mantle-derived volatiles can explain the general characteristics of ³He/⁴He ratios, δ¹³C values, and CO₂/³He ratios at the nine sample locations; (2) preferential degassing of He from the geothermal waters is responsible for variations in CO₂/³He values and He contents at each sample location; and (3) CO₂ dissolution followed by calcite precipitation is responsible for variations in CO₂ contents and δ¹³C values at most locations. For each of the geochemical parameters, anomalies are defined in the temporal record by values that fall outside two standard deviations of average values at each specific location. Geochemical anomalies that may be related to seismic activity are recorded on June 28, 2004 at Yalova, where a M = 4.2 earthquake occurred 43 days earlier at 15 km distance from the sample location, and on April 7, 2003 at Efteni, where a M = 4.0 earthquake occurred 44 days later at a distance of 12 km. At both locations, the sampling periods containing geochemical anomalies were preceded by an increase in M ? 3 earthquakes occurring within 60 days and less than 40 km distance.     

Comparison of stable isotopes,ratios of Cl/Cl and I/I in brine and deep groundwater from the Pacific coastal region and the eastern margin of the Japan Sea

Fifty-three samples, including brines associated with oil and natural gas reservoirs and groundwater samples from deep boreholes, were collected from the Pacific and Japan Sea coastal regions in Japan. The ¹²⁹I/¹²⁷I and ³⁶Cl/Cl ratios, and stable isotopes (δD and δ¹⁸O) are compared to investigate differences related to the geotectonic settings of the two regions. The δD and δ¹⁸O data indicate that brine and groundwater from the Pacific coastal region reflect mixing of meteoric water with connate seawater in the pores of sedimentary rocks. On the other hand, brine and groundwater from the Japan Sea coastal region have been hydrothermally altered. In particular, brines associated with petroleum accumulations at Niigata and Akita showed the same isotopic characteristics as fluids found in the Kuroko deposits of the Green Tuff region in northeastern Japan. There is little difference in the ³⁶Cl/Cl ratios in brine and groundwater from the Pacific and Japan Sea coasts. Most brine and some deep groundwater, except those from the Pleistocene Kazusa Group, have already reached the average secular equilibrium ratio of 9.9 ± 2.7 × 10⁻¹⁵ for their mudstone and sandstone reservoirs. There was no correlation between the ³⁶Cl/Cl ratios and differences in geotectonic setting between the Pacific and the Japan Sea coast. The molar I/Br ratio suggests that the I in all of water samples was of biogenic origin. The average ¹²⁹I/¹²⁷I ratio was 290 ± 130 × 10⁻¹⁵ to 294 ± 105 × 10⁻¹⁵ in both regions, showing no relationship to the different geotectonic settings. The uncontaminated brine and groundwater samples are likely to have retained the original ¹²⁹I/¹²⁷I ratios of marine I released from the old organic matter stored in sedimentary rock.     

Os and Os enrichments and high-He/He sources in the Earth’s mantle: Evidence from Icelandic picrites

Picrites from the neovolcanic zones in Iceland display a range in ¹⁸⁷Os/¹⁸⁸Os from 0.1297 to 0.1381 (γ_Os = + 2.1 to +8.7) and uniform ¹⁸⁶Os/¹⁸⁸Os of 0.1198375 ± 32 (2σ). The value for ¹⁸⁶Os/¹⁸⁸Os is within uncertainty of the present-day value for the primitive upper mantle of 0.1198398 ± 16. These Os isotope systematics are best explained by ancient recycled crust or melt enrichment in the mantle source region. If so, then the coupled enrichments displayed in ¹⁸⁶Os/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os from lavas of other plume systems must result from an independent process, the most viable candidate at present remains core-mantle interaction. While some plumes with high ³He/⁴He, such as Hawaii, appear to have been subjected to detectable addition of Os (and possibly He) from the outer core, others such as Iceland do not.A positive correlation between ¹⁸⁷Os/¹⁸⁸Os and ³He/⁴He from 9.6 to 19 Ra in Iceland picrites is best modeled as mixtures of 1 Ga or older ancient recycled crust mixed with primitive mantle or incompletely degassed depleted mantle isolated since 1-1.5 Ga, which preserves the high ³He/⁴He of the depleted mantle at the time. These mixtures create a hybrid source region that subsequently mixes with the present-day convecting MORB mantle during ascent and melting. This multistage mixing scenario requires convective isolation in the deep mantle for hundreds of million years or more to maintain these compositionally distinct hybrid sources. The ³He/⁴He of lavas derived from the Iceland plume changed over time, from a maximum of 50 Ra at 60 Ma, to approximately 25-27 Ra at present. The changes are coupled with distinct compositional gaps between the different aged lavas when ³He/⁴He is plotted versus various geochemical parameters such as ¹⁴³Nd/¹⁴⁴Nd and La/Sm. These relationships can be interpreted as an increase in the proportion of ancient recycled crust in the upwelling plume over this time period.The positive correlation between ¹⁸⁷Os/¹⁸⁸Os and ³He/⁴He demonstrates that the Iceland lava He isotopic compositions do not result from simple melt depletion histories and consequent removal of U and Th in their mantle sources. Instead their He isotopic compositions reflect mixtures of heterogeneous materials formed at different times with different U and Th concentrations. This hybridization is likely prevalent in all ocean island lavas derived from deep mantle sources.     

Predicting the impact of land use on the major element and nutrient fluxes in coastal Mediterranean rivers: The case of the Têt River (Southern France)

This study presents a detailed discrimination between the natural and anthropogenic sources of dissolved major elements in the Têt River, a typical small coastal river in the south of France. The main objectives were to quantify the materials that were released by human activities in the basin, and to determine the specific element inputs for the major land use forms. The dissolved material fluxes were estimated by weekly monitoring over a hydrological year (2000–2001) along the major water gauging stations, and the flux relationships were examined in the context of anthropogenic and natural basin characteristics as determined by a Geographical Information System (GIS). Intensive agricultural land use in the form of fruit tree cultures and vineyards has a strong control on the dissolved element fluxes in the river. Area specific element releases for these cultures are greatest for SO₄, with an estimated average of about 430 ± 18 keq km⁻² a⁻¹. This is ?11 times the natural SO₄ release by rock weathering. Also for K, NO₃, PO₄ and Mg, the specific releases were ?6 times the natural weathering rates (respectively about 44, 60, 4 and 265 keq km⁻² a⁻¹). Waste-waters are the other major source of anthropogenic elements in the river. They have an important role for the fluxes of inorganic P and N, but they are also a considerable source of Cl and Na to the river. For example, the average annual release of Cl is around 150 moles/inhabitant in the rural basin parts. Further downstream, however, where population density strongly increases, industrial effluents can enhance this value (>300 moles/inhabitant). The waste-waters contribute more than 70% of the dissolved inorganic N export to the sea, although their contribution to the average DOC export is almost negligible (3%).     

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.     

Helium isotopic fingerprints of the heavy land subsidence left in groundwater of the Saga Plain,near Beppu–Shimabara graben,Kyushu, Japan

The Saga Plain is near Beppu–Shimabara graben, a region of potential active volcanism. In the graben, mantle He, which has a high ³He/⁴He ratio of 1.1 × 10⁻⁵, escapes easily from the underlying subduction zone. In groundwater of the Saga Plain, except in the Shiroishi district, this ratio gradually increased as the dissolved He content increased, to a maximum of 5 × 10⁻⁶. In central Shiroishi, however, the ratio reached a minimum of 8.7 × 10⁻⁷ with increasing dissolved He content, suggesting that groundwater in central Shiroishi has selectively accumulated radiogenic He, which has a very low ratio of 1 × 10⁻⁸, rather than reflecting the regional He, which is rich in mantle He. This can be explained if groundwater in Shiroishi has become mixed with fossil pore water drawn from impermeable marine clay aquitard layers. The withdrawal of pore water has also caused severe land subsidence in central Shiroishi.     

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.     

Canadian Shield brine from the Con Mine, Yellowknife, NT, Canada: Noble gas evidence for an evaporated Palaeozoic seawater origin mixed with glacial meltwater and Holocene recharge

Dissolved noble gas concentrations were measured in high salinity (270 g/L) Ca(Na)-Cl groundwaters from the Con Mine, Yellowknife, Canada in an effort to discriminate between two possible origins, as either a brine generated by evaporative enrichment in a Paleozoic inland sea, or marine water concentrated by freezing during glacial times. Major ion and isotope geochemistry indicate that brines from the deepest level remain relatively undisturbed by mixing with modern water introduced by mining. Mixing calculations are used to quantify fractions of brine, glacial meltwater and modern water. From this, noble gas concentrations were corrected for excess air with Ne and normalized to 100% brine solution. Over-pressuring of helium and argon in the brine provide age constraints based on the accumulation of geogenic ⁴He and ⁴⁰Ar. Radiogenic age calculations together with the local geological history suggest brine emplacement during early Palaeozoic time, likely during the Devonian when evaporitic inland seas existed in this region. The concentrations of the atmospherically derived noble gases in the brine fraction (Kr = 1.4E-8, Xe = 8.5E-10 cc_STP/cc_H2O) are close to atmospheric equilibrium for brine at 25 °C (Kr = 7.3E-9, Xe = 8.0E-10 cc_STP/cc_H2O), but are far lower than would be expected for closed-system concentration of seawater by freezing (Kr = 2.8E-6, Xe = 4.2E-7 cc_STP/cc_H2O). Thus, despite the complicated mixing history of the brine, the atmospheric and geogenic noble gases provide strong evidence for an origin as air-equilibrated brine from evaporated Paleozoic seawater, which infiltrated via density displacement through existing fractures and faults into the Canadian Shield.     

He,Sr and Nd isotopic variations in lavas from the juan fernandez archipelago,SE pacific

Helium, Sr, and Nd isotopic ratios and major and trace element compositions have been measured on a suite of lavas from the intra-plate volcanos of the Juan Fernandez Archipelago, Chile. Lavas from the islands of Mas Afuera and Mas a Tierra and from Monte Alpha and Friday seamounts have Sr and Nd isotopic ratios lying on the low¹⁴³Nd/¹⁴⁴Nd side of the mantle array (⁸⁷Sr/⁸⁶Sr:0.7034–0.7037;¹⁴³Nd/¹⁴⁴Nd:0.51281–0.51289). The homogeneity of these tracers suggests the involvement of a restricted range of mantle source compositions throughout Juan Fernandez volcanism. In marked contrast is the large range in³He/⁴He, from 7.8 to 18.0 R_A. A bimodal³He/⁴He distribution on Mas a Tierra is associated with two distinct volcanic lineages;³He/⁴He ratios of 14.5–18.0 R_A (n=15) occur in alkalic and tholeiitic shield basalts, whereas post-shield basanites range from 11.2 to 13.6 R_A (n=12). Elemental and isotopic systematics demonstrate a transition from an enriched (Loihi-like) plume source in the shield lavas to a more MORB-like source in the post-shield volcanics. The transition between these sources is much more pronounced in³He/⁴He than in the other isotopic tracers. The predominantly tholeiitic basalts of Mas Afuera have exceptionally uniform isotopic and elemental characteristics; Sr and Nd ratios are similar to those of Mas a Tierra, but³He/⁴He ratios are lower and more uniform at 8.3±0.5 R_A (n=17). The dramatic distinction between Mas Afuera and Mas a Tierra helium is surprising given the great similarity between the two islands in other geochemical characteristics. Both the Mas Afuera and Mas a Tierra results demonstrate that helium records systematic processes not readily apparent from other isotopic or elemental indicators. Neither magma chamber degassing nor local metasomatic events are likely to be responsible. We suggest that the observed variations may be attributed to mixing of plume and asthenospheric sources in which the plume component is characterized by a heterogeneous distribution of volatiles or has suffered extraction of small degree partial melts prior to mixing.     

Geochemistry of volcanic and hydrothermal fluids and volatile budget of the Kamchatka-Kuril subduction zone

A data base for the composition and emission rates of more than 100 thermal manifestations including boiling geothermal systems and 23 volcanoes along the 1900 km long Kamchatka-Kuril (KK) arc is presented. These results were used to estimate mean fluxes of volatiles from the KK arc. The fluxes from the KK arc are compared with the fluxes from the best studied Central American (CA) arc and with the compiled literature data on global fluxes. The error ranges and the OUT/IN (in)balance calculations are also discussed. The estimated fluxes of volatiles from volcanic fumaroles and the observed, normalized to the Cl content, fluxes from hydrothermal systems are very close, with the higher hydrothermal flux from Kuril Islands due to a larger number of the acidic Cl-SO₄ springs on the Islands and their outflow rates. The total volcanic SO₂ flux from the whole KK arc is estimated to be higher than 3000 t/d. The measured S and C fluxes from hydrothermal systems are much lower than the volcanic output due to the loss of these components in the upper crust (mineral precipitation). The Cl/³He ratio is inferred to be a stable indicator of the arc setting for hydrothermal and volcanic fluids with a mean value of (2 ± 4) × 10⁹. Comparison of the obtained volcano-hydrothermal fluxes with fluxes calculated from the erupted solid volcanic products at Kamchatka and Kurils during Holocene time reveals that the total estimated volatile output from the KK arc is compatible with the total magmatic output if the intruded to erupted ratio is close to 7, i.e. almost the same as assumed for the Central American arc. Calculated fluxes as well as the ratios for OUT/IN fluxes (volcanic + hydrothermal output/slab + mantle input) for CO₂, S, H₂O, Cl, N₂, ⁴He and ³He from the KK arc normalized to the arc length are in general close to the global estimates. The fractions of CO₂ and S in the total volatile output at KK arc derived directly from the mantle wedge are 18% and 16% (mole basis), respectively. Fractions of mantle derived H₂O, N₂ and Cl are much lower, less that 5% of their output.