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.     

Inert gas patterns in the regolith at the Apollo 15 landing site

He, Ne, Ar, Kr and Xe were measured mass spectrometrically in eight bulk fines and one sample of 2–4 mm fines (15603) from stations LM-ALSEP, 2, 6, 6¹, 7^a, and 9. We have also measured these gases in size fractions of samples 15091 and 15601. These samples come from three morphologically distinct selenographic settings: the Appenine Front, the Mare and Hadley Rille. Measured gas contents in these samples are comparable to those from previous Apollo missions. He⁴ and the other trapped gases are inversely proportional to grain diameter in the size fractions of 15091 and 15601. More than 90 per cent of the trapped gas in 15601 is surface correlated; hence is probably directly implanted solar wind. Size fractions of 15091 contain large volume correlated amounts of He⁴, Ne²⁰ and Ar³⁶. He⁴/Ne²⁰ ranges from about 20 to 60; Ne²⁰/Ar³⁶ from 5 to 8: Ar³⁶/Kr⁸⁴ from 2400 to 3200; and Kr⁸⁴/Xe¹³² from 3·2 to 7·3. The lowest He⁴/Ne²⁰ ratios occur in samples rich in green glass spherules which have He⁴/Ne²⁰ ≤ 10 (Lakatos, Heymann, and Yaniv, unpublished). He⁴/He³ ranges from about 210 to 2700; Ne²⁰/Ne²² from 12·7 to 13·2; Ne²¹/Ne²² from 0·035 to 0·041; and Ar³⁶/Ar³⁸ from 5·26 to 5·45. The measured Ar⁴⁰/Ar³⁶ ratios range from 0·757 to 3·56; when corrected for radiogenic Ar⁴⁰, the range becomes 0·6 to 3·4. The largest corrected Ar⁴⁰/Ar³⁶ ratios occur in samples from the Apennine Front, the smallest occur in the Mare. This could be due to slope effects between the front as opposed to the mare terrain. An alternative possibility is that the Front fines acquired their atmospheric Ar⁴⁰ at a time when the concentration of neutral Ar⁴⁰ in the lunar atmosphere was relatively large.Ne²¹ radiation ages were calculated for all samples. There is evidence in the landing area for debris from craters with ages less than 100 × 10⁶ yr, but these craters cannot be firmly identified from the data.     

Ar loss in experimentally deformed muscovite and biotite with implications for Ar/Ar geochronology of naturally deformed rocks

The effects of deformation on radiogenic argon (⁴⁰Ar^∗) retentivity in mica are described from high pressure experiments performed on rock samples of peraluminous granite containing euhedral muscovite and biotite. Cylindrical cores, ∼15 mm in length and 6.25 mm in diameter, were drilled from granite collected from the South Armorican Massif in northwestern France, loaded into gold capsules, and weld-sealed in the presence of excess water. The samples were deformed at a pressure of 10 kb and a temperature of 600 °C over a period 29 of hours within a solid medium assembly in a Griggs-type triaxial hydraulic deformation apparatus. Overall shortening in the experiments was approximately 10%. Transmitted light and secondary and backscattered electron imaging of the deformed granite samples reveals evidence of induced defects and for significant physical grain size reduction by kinking, cracking, and grain segmentation of the micas.Infrared (IR) laser (CO₂) heating of individual 1.5-2.5 mm diameter grains of muscovite and biotite separated from the undeformed granite yield well-defined ⁴⁰Ar/³⁹Ar plateau ages of 311 ± 2 Ma (2σ). Identical experiments on single grains separated from the experimentally deformed granite yield results indicating ⁴⁰Ar^∗ loss of 0-35% in muscovite and 2-3% ⁴⁰Ar^∗ loss in biotite. Intragrain in situ ultraviolet (UV) laser ablation ⁴⁰Ar/³⁹Ar ages (±4-10%, 1σ) of deformed muscovites range from 309 ± 13 to 264 ± 7 Ma, consistent with 0-16% ⁴⁰Ar^∗ loss relative to the undeformed muscovite. The in situ UV laser ablation ⁴⁰Ar/³⁹Ar ages of deformed biotite vary from 301 to 217 Ma, consistent with up to 32% ⁴⁰Ar^∗ loss. No spatial correlation is observed between in situ⁴⁰Ar/³⁹Ar age and position within individual grains. Using available argon diffusion data for muscovite the observed ⁴⁰Ar^∗ loss in the experimentally treated muscovite can be utilized to predict average ⁴⁰Ar^∗ diffusion dimensions. Maximum ⁴⁰Ar/³⁹Ar ages obtained by UV laser ablation overlap those of the undeformed muscovite, indicating argon loss of <1% and an average effective grain radius for ⁴⁰Ar^∗ diffusion ?700 μm. The UV laser ablation and IR laser incremental ⁴⁰Ar/³⁹Ar ages indicating ⁴⁰Ar^∗ loss of 16% and 35%, respectively, are consistent with an average diffusion radius ?100 μm. These results support a hypothesis of grain-scale ⁴⁰Ar^∗ diffusion distances in undeformed mica and a heterogeneous mechanical reduction in the intragrain effective diffusion length scale for ⁴⁰Ar^∗ in deformed mica. Reduction in the effective diffusion length scale in naturally deformed samples occurs most probably through production of mesoscopic and submicroscopic defects such as, e.g., stacking faults. A network of interconnected defects, continuously forming and annealing during dynamic deformation likely plays an important role in controlling both ⁴⁰Ar^∗ retention and intragrain distribution in deformed mica. Intragrain ⁴⁰Ar/³⁹Ar ages, when combined with estimates of diffusion kinetics and distances, may provide a means of establishing thermochronological histories from individual micas.     

Rare gas isotopic composition of natural gases

One hundred natural gas samples of different geological periods collected from various localities were determined for their nitrogen, helium and argon contents as well as the isotopic composition of argon. The ratio Ar⁴⁰/Ar³⁶ was found to be from 305 to 9,255. A current heliumargon chronological formula for calculating natural gas ages was corrected. Instead, based upon the chronological accumulating effect of radiogenic Ar⁴⁰, an Ar⁴⁰-Ar³⁹ empirical formula for calculating natural gas ages has been proposed. It can be seen from the ratio of nitrogen to atmospheric argon that most of the nitrogen in these natural gases could not be derived from atmospheric nitrogen. The range of radiogenic He/Ar⁴⁰ is from 5.19 to 23. 18, and that for most samples from 7 to 14. The He/Ar⁴⁰ ratios of Sinian samples are from 5.39 to 6.14, indicating their derivation from the deep interior of the earth. It should be noted that the Ar⁴⁰/Ar³⁶ ratio shows a general trend of approaching the atmospheric value from the Sinian to the Tertiary period, or from old to young in geological age, mirroring, to a great extent, the evolutionary tendency of the rare gas isotopic composition of natural gases with continuous degassing of the earth.     

Multiple atmospheric noble gas components in hydrocarbon reservoirs: a study of the Northwest Shelf, Delaware Basin, SE New Mexico

The Northwest Shelf of the Delaware Basin, SE New Mexico is the site of several large and productive oil and gas fields. The most productive reservoirs are located in the late Pennsylvanian Morrow and early Permian Abo formations. Production from the latter more important play is predominately from fluvial Abo red beds of the Pecos Slope Field. The oxidizing conditions implied by the reddish color of the formation require an external hydrocarbon source. To test the existing migration model for the region and constrain the location of potential hydrocarbon sources, we measured the elemental and isotopic composition of noble gases produced along with the hydrocarbons. We found the hydrocarbons to be highly enriched in radiogenic ⁴He, ⁴⁰*Ar and nucleogenic ²¹*Ne [F(⁴He) = 44,000-250,000; ⁴⁰Ar/³⁶Ar = 400-3145; ²¹Ne/²²Ne = 0.044-0.071]. The greatest enrichments occur in the Pecos Slope gas fields. The hydrocarbons also contain three independent nonradiogenic noble gas components each with an atmospheric isotopic composition. One component is most likely air-saturated water (ASW). The second component is enriched in the heavy noble gases [F(¹³⁰Xe) > 8.5] and is derived from the hydrocarbon sources. The third component is enriched in Ne [F(²⁰Ne) > 0.8] that we believe is degassed from sources within the reservoirs. This component is correlated with but decoupled from the dominant source of radiogenic ⁴He and ⁴⁰*Ar. Very high concentrations of ⁴He (up to ∼1% by volume) in the Pecos slope reservoirs require a source external to the reservoirs, such as the underlying Precambrian basement granites and sedimentary equivalents. Structural buckles cutting through the Pecos field may act as high flux vertical pathways for the radiogenic ⁴He. If the hydrocarbons in the Pecos slope fields have migrated northward from the deeper Delaware Basin, as suggested by compositional trends, then perhaps the buckles also play an important role in the distribution and filling of the Pecos slope reservoirs.     

Plume-ridge interaction along the Galapagos Spreading Center: discerning between gas loss and source effects using neon isotopic compositions and He-Ar-CO2 relative abundances

To document the plume-ridge interaction at the Galapagos Spreading Center (GSC), we present neon 3-isotope analyses performed on vesicles-trapped volatiles of MORB glasses dredged along the ridge axis between 86°W and 98°W. ⁴He-⁴⁰Ar^∗-CO₂ relative abundances were also measured in order to study gas loss in this context and discern between source and degassing effects. Neon isotopic compositions are in the MORB range with ²¹Ne/²²Ne ratios extrapolated to the ²⁰Ne/²²Ne mantle ratio of 12.5 varying between 0.053 and 0.072. Unradiogenic plume-like compositions were not measured. The ⁴He-⁴⁰Ar^∗-CO₂ relative abundances are highly variable along the ridge, for example ⁴He/⁴⁰Ar^∗ ratio varies between 3 and 433, but these variations can be fully explained by a simple model of Rayleigh distillation, with a single volatile source composition for the entire GSC. Magma fractional crystallisation, which increases in the plume influenced zone, seems to be the main motor for degassing. As other geochemical and geophysical studies indicate a significant plume influence on the GSC, these results suggest the plume component feeding the ridge is either degassed or else different from the plume core.     

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.     

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.     

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.     

Intensive sampling of noble gases in fluids at Yellowstone: I. Early overview of the data; regional patterns

The Roving Automated Rare Gas Analysis (RARGA) lab of Berkeley's Physics Department was deployed in Yellowstone National Park for a 19 week period commencing in June, 1983. During this time 66 gas and water samples representing 19 different regions of hydrothermal activity within and around the Yellowstone caldera were analyzed on site. Routinely, the abundances of five stable noble gases and the isotopic compositions of He, Ne, and Ar were determined for each sample. In a few cases the isotopes of Kr and Xe were also determined and found to be of normal atmospheric constitution.Correlated variations in the isotopic compositions of He and Ar can be explained within the precision of the measurements by mixing of only three distinct components. The first component is of magmatic origin and is enriched in the primordial isotope ³He with ${}^3\text{He}{}^4\text{He}\text{≥ 16}$ times the air value. This component also contains radiogenic ⁴⁰Ar and possible ³⁶Ar with ${}^{40}\text{Ar}{}^{36}\text{Ar}\text{≥ 500}$, resulting in a ${}^3\text{He}{}^{36}\text{Ar}$ ratio ≥ 41,000 times the air value. The second component is assumed to be purely radiogenic ⁴He and ⁴⁰Ar (${}^{41}\text{He}{}^{401}\text{Ar}\text{= 4.08 ± .33}$). This component is the probable carrier of observed excesses of ²¹¹Ne, attributed to the α,n reaction on ¹⁸O. Its radiogenic character implies a crustal origin in U. Th, and Krich aquifer rocks. The third component, except for possible mass fractionation, is isotopically indistinguishable from the noble gases in the atmosphere. This component originates largely from infiltrating run-off water saturated with atmospheric gases.In addition to exhibiting nucleogenic ²¹¹Ne, Ne data show anomalies in the ratio ${}^{20}\text{Ne}{}^{20}\text{Ne}$, which correlate roughly with the ${}^{21}\text{Ne}{}^{22}\text{Ne}$ anomalies for the most part, but not as would occur from simple mass fractionation. Some exaggerated instances of the ${}^{20}\text{Ne}{}^{22}\text{Ne}$ anomaly occur which could be explained by combined mass fractionation of Ne and Ar isotopes to a severe degree coupled with remixing with normally isotopic gases. Otherwise exotic processes have to be invoked to explain the ²⁰Ne data.Relative abundances of the non-radiogenic and non-nucleogenic noble gases (²²Ne, ³⁶Ar, ⁸⁴Kr, and ¹³²Xe) are highly variable but strongly correlated. High Xe/Ar ratios are always accompanied by low Ne/ Ar ratios and vice versa. Except for water from the few cold (T < 20°C) springs analyzed, none of the samples have relative abundances consistent with air saturated water and the observed variations are not readily explained by the distillation of air saturated water.In characterizing each area of hydrothermal activity by the highest ${}^3\text{He}{}^4\text{He}$ ratio found for that area, we find that within the caldera this parameter is somewhat uniform at ~7 ± 1 times the air value. There are exceptions, most notably at Mud Volcano, an area located along a crest of recent and rapid uplift. Here the maximum ${}^3\text{He}{}^4\text{He}$ ratio is ~ 16 times the air value. Also noteworthy is Gibbon Basin which is in the vicinity of the most recent rhyolitic volcanism and exhibits a ${}^3\text{He}{}^4\text{He}$ ratio ~ 13 times the air value. Immediately outside the caldera the maximum $\text{sol}{}^3\text{He}{}^4\text{He}$ ratio decreases rapidly to values < ~3 times the air value.     

Origin and geochemical reaction paths of sabkha brines: Sabkha Jayb Uwayyid, eastern Saudi Arabia

Sabkhas are ubiquitous geomorphic features in eastern Saudi Arabia. Seven brine samples were taken from Sabkha Jayb Uwayyid in eastern Saudi Arabia. Brine chemistry, saturation state with respect to carbonate and evaporate minerals, and evaporation-driven geochemical reaction paths were investigated to delineate the origin of brines and the evolution of both brine chemistry and sabkha mineralogy. The average total dissolved solids in the sabkha brines is 243 g/l. The order of cation dominance is Na⁺   >>  Mg²⁺ >>  Ca²⁺>K⁺, while anion dominance is Cl⁻ >> SO₄ ²⁻ >> HCO₃ ⁻. Based on the chemical divide principle and observed ion ratios, it was concluded that sabkha brines have evolved from deep groundwater rather than from direct rainfall, runoff from the surroundings, or inflow of shallow groundwater. Aqueous speciation simulations show that: (1) all seven brines are supersaturated with respect to calcite, dolomite, and magnesite and undersaturated with respect to halite; (2) three brines are undersaturated with respect to both gypsum and anhydrite, while three brines are supersaturated with respect to both minerals; (3) anhydrite is a more stable solid phase than gypsum in four brines. Evaporation factors required to bring the brines to the halite phase boundary ranged from 1.016 to 4.53. All reaction paths to the halite phase boundary follow the neutral path as CO₂ is degassed and dolomite precipitates from the brines. On average, a sabkha brine containing 1 kg of H₂O precipitates 7.6 g of minerals along the reaction path to the halite phase boundary, of which 52% is anhydrite, 35.3% is gypsum, and 12.7% is dolomite. Bicarbonate is the limiting factor of dolomite precipitation, and sulfate is the limiting factor of gypsum and anhydrite precipitation from sabkha brines.     

Linking groundwater quality to residence times and regional geology in the St. Lawrence Lowlands,southern Quebec,Canada

The assessment of groundwater quality in shallow aquifers is of high societal relevance given that large populations depend directly on these water resources. The purpose of this study was to establish links between groundwater quality, groundwater residence times, and regional geology in the St. Lawrence Lowlands fractured bedrock aquifer. The study focuses on a 4500 km² watershed located in the St. Lawrence Lowlands of the province of Quebec in eastern Canada. A total of 150 wells were sampled for major, minor, and trace ions. Tritium (³H) and its daughter element, ³He, as well as radiocarbon activity (A¹⁴C) were measured in a subset of wells to estimate groundwater residence times. Results show that groundwater evolves from a Ca–HCO₃ water type in recharge zones (i.e., the Appalachian piedmont) to a Na–HCO₃ water type downgradient, toward the St. Lawrence River. Locally, barium (Ba), fluoride (F), iron (Fe), and manganese (Mn) concentrations reach 90, 2, 18, and 5.9 mg/L respectively, all exceeding their respective Canadian drinking water limits of 1, 1.5, 0.3, and 0.05 mg/L. Release of these elements into groundwater is mainly controlled by the groundwater redox state and pH conditions, as well as by the geology and the duration of rock–water interactions. This evolution is accompanied by increasing ³H/³He ages, from 4.78 ± 0.44 years upgradient to more than 60 years downgradient. Discrepancies between calculated ³H/³He and ¹⁴C water ages (the latter ranging from 280 ± 56 to 17,050 ± 3410 years) suggest mixing between modern water and paleo-groundwater infiltrated through subglacial recharge when the Laurentide Ice Sheet covered the study area, and during the following deglaciation period. A linear relationship between ³H activity and corrected ¹⁴C versus Mg/Ca and Ba support a direct link between water residence time and the chemical evolution of these waters. The Ba, F, Fe, and Mn concentrations in groundwater originate from Paleozoic rocks from both the St. Lawrence Platform and the Appalachian Mountains. These elements have been brought to the surface by rising hydrothermal fluids along regional faults, and trapped in sediment during their deposition and diagenesis due to reactions with highly sulfurous and organic matter-rich water. Large-scale flow of meltwater during subglacial recharge and during the subsequent retreat of the Laurentide Ice Sheet might have contributed to the leaching of these deposits and their enrichment in the present aquifers. This study brings a new and original understanding of the St. Lawrence Lowlands groundwater system within the context of its geological evolution.     

四川盆地龙女寺储卤构造深层地下卤水的水文地球化学特征及成因

本文将龙女寺储卤构造深层地下卤水与不同浓缩阶段的黄海水两者的化学组分进行比较,以及对不同储卤层卤水之间的化学组分进行比较,结果表明该储卤构造地下卤水以高矿化度和富含Br,I,Sr,Ba等元素为特征,可分为两种类型,即碎屑岩储卤层的Cl NaCa型卤水和碳酸盐岩储卤层的Cl Na型卤水。前者来源于以陆相为主的同生沉积水,泥岩和页岩的隔膜渗滤作用可能对卤水化学组分的富集有着重要的影响;而后者则来源于海相同生沉积残余卤水,其化学组分主要受蒸发岩沉积的控制     

Chemistry of petroleum brines from oil-producing wells in Cretaceous rocks from Southeast Mexico

Brine chemical data obtained from oil wells in Cretaceous oilfields in the Southeastern Basin of Mexico show a complex evolution, with the following main hydrochemical processes: (1) mixing of highly evaporated brines, past the point of halite precipitation with seawater; (2) water/rock interactions between brines and carbonated rocks (dolostones).     

Geochemistry and genesis of brine emanations from Cretaceous strata of the Mamfe Basin, Cameroon

The geochemistry of 5 salt springs in the southwestern Mamfe Basin was investigated in order to infer the mineral content of their source and to relate the genesis of the springs to the local geology. Field observations revealed that, they are cold springs (23–28 °C), and are composed of secondary brines that are neutral to alkaline with pH values ranging from 7 to 8.7. Results of chemical analysis show that the springs contain major ions that form evaporite minerals, as well as chalcophile elements. The dominant cation is Na⁺ (>96%), and the dominant anion is Cl⁻ (>99%). Based on correlation coefficients between ions that form evaporites and field occurrence of efflorescences of halite, it is suggested that the ancient evaporites in the Mamfe Basin are composed entirely of carbonate and chloride salts. Meteoric and convective fluid flow processes are responsible for the dissolution of ancient evaporites and subsequent migration of brines to the surface from underground. The brines migrate through permeable strata with migration pathways resulting from a combination of fracture porosity created by post––Cretaceous tectonism and intergranular porosity enhanced by the chemically aggressive migrating brines.     

Solubility controlled noble gas fractionation during magmatic degassing: Implications for noble gas compositions of primary melts of OIB and MORB

Noble gas abundances in basaltic glasses from ocean islands (OIBs) are generally lower than those of mid-oceanic ridge basalts (MORBs), contrary to most geodynamic models which usually require that the source of OIBs is less degassed (resulting in higher primordial noble gas abundances) and more trace element enriched (resulting in higher radiogenic noble gas abundances) than the MORB source. Therefore, noble gas abundances in OIBs are often thought to have been reduced by extensive gas loss from the magma before eruption.The extent of magmatic degassing can be tested as it will cause characteristic changes in the composition of the volatiles; notably the ⁴He/⁴⁰Ar* ratio (where ⁴⁰Ar* is ⁴⁰Ar corrected for atmospheric contamination) will increase in residual volatiles due to the higher solubility of He relative to Ar. The degree of He-Ar fractionation for a given fraction of gas loss depends on the ratio of the solubilities, S_He/S_Ar, which is sensitive to (among other things) the CO₂ and H₂O content of the basalt at the time of degassing.From a global database of OIB and MORB glasses, we show that ⁴He/⁴⁰Ar* ratios of MORB glasses are broadly consistent with degassing of a magma with an initial ⁴⁰Ar of ≈1.5 × 10⁻⁵ ccSTP/g, i.e., similar to that of the “popping rock.” However, OIB glasses generally have lower ⁴⁰Ar* concentration for a given ⁴He/⁴⁰Ar*. While this would appear to require lower ⁴⁰Ar* abundances in the undegassed OIB magmas, the higher volatile contents of OIBs will reduce S_He/S_Ar (relative to MORBs) during degassing. By modeling S_He/S_Ar in OIBs, it is possible to show that extensive degassing of OIBs can occur without dramatically increasing the ⁴He/⁴⁰Ar* ratio. We show that undegassed ⁴⁰Ar concentrations of OIB magmas were probably similar to those of MORBs.     

Inert gases in a terra sample: measurements in six grain-size fractions and two single particles from Luna 20

The inert gases have been measured in six size fractions covering the range below 500 μm, in a single feldspathic fragment weighing 523 μg, and in an agglutinate particle weighing 465 μg. The two size fractions between 125 and 250 μm as well as 250 and 500 μm were separated into magnetic and non-magnetic portions, which were measured separately. Like the Apollo and Luna 16 fines, the terra fines represented by Luna 20 are very rich in trapped solar-wind gases, but they contain relatively less He⁴ and Ne²⁰, which is revealed by their average $\text{He}{}^4\text{Ne}{}^{20}$ ratio of 35 and $\text{Ne}{}^{20}\text{Ar}{}^{36}$ ratio of 2.9. Obviously the terra materials are less retentive for solar-wind He and Ne than typical mare fines such as 10084. Whether this is due to the relatively small TiO₂ or the relatively large plagioclase content of the former is not resolved. ($\text{Ar}{}^{36}\text{Kr}{}^{84}\text{)}{}_{\mathrm{trapped}}$ and ($\text{Ar}{}^{36}\text{Xe}{}^{132}\text{)}{}_{\mathrm{trapped}}$ ratios are relatively large; the average values are 2800 and 14400, respectively. The apparent Ne²¹ radiation ages of all the size fractions are in the range 209–286 × 10⁶ yr; the average is 260 × 10⁶ yr. This is in the range of values known for the Apollo and Luna 16 fines. The feldspathic fragment has a much greater apparent Ne_c²¹ age of 780 × 10⁶ yr. The Ar⁴⁰-Ar³⁶ systematic reveals the presence of two Ar⁴⁰ components, because Ar⁴⁰ = (1.41 ± 0.076)Ar³⁶ + (0.490 ± 0.130) × 10^?4 (cm³ STP/g). The $\text{Ar}{}^{40}\text{Ar}{}^{36}$ slope of 1.41 is not inconsistent with an origin of the sample from a relatively old terra region.     

Part II. Evaluation of Ar-Ar quartz ages: Implications for fluid inclusion retentivity and determination of initial Ar/Ar values in Proterozoic samples

The argon isotope systematics of vein-quartz samples with two different K-reservoirs have been evaluated in detail. Potassium is hosted by ultra-high-salinity fluid inclusions in quartz samples from the Eloise and Osborne iron-oxide-copper-gold (IOCG) deposits of the Mt Isa Inlier, Australia. In contrast, K is hosted by accidentally trapped mica within lower-salinity fluid inclusions of a sample selected from the Railway Fault, 13 km south of the Mt Isa copper mine, Australia. Imprecise apparent ages have been obtained for all of the samples studied and conclusively demonstrate that quartz fluid inclusions are retentive to Ar and have not leaked over billions of years. IOCG samples that host K in fluid inclusions only, have K/Cl values of <1 and the ages obtained represent the maximum ages for mineralization. In contrast, the Railway Fault samples that include accidentally trapped mica have K/Cl values of ?1. Excess ⁴⁰Ar_E plus Cl hosted by fluid inclusions, and radiogenic ⁴⁰Ar_R plus K, are strongly correlated in these samples and define a plane in 3D ⁴⁰Ar-³⁶Ar-K-Cl space. In this case, the plane yields an ‘excess ⁴⁰Ar_E’ corrected age of ∼1030 Ma that is 100’s of Ma younger than nearby Cu-mineralization at Mt Isa. The age is interpreted to reflect ⁴⁰Ar-loss from the accidentally trapped mica into the surrounding fluid inclusions, and is not related to the samples’ age of formation. The initial ⁴⁰Ar/³⁶Ar value of fluid inclusions is widely used to provide information on fluid origin. For the IOCG samples that host K in fluid inclusions only, the initial ⁴⁰Ar/³⁶Ar values are close to the measured values at every temperature of stepped heating experiments. For samples that include accidentally trapped mica, the correction for post-entrapment radiogenic ⁴⁰Ar_R production is significant. Furthermore, because ³⁹Ar_K present in accidentally trapped mica crystals is released at different temperatures to radiogenic ⁴⁰Ar_R lost to the surrounding fluid inclusions, intra-sample ⁴⁰Ar/³⁶Ar variation cannot be reliably documented. The results demonstrate that noble gas analysis is readily applicable to Proterozoic, or older, samples but that if K-mineral impurities are present within quartz the abundance of K must be determined before calculation of mean ⁴⁰Ar/³⁶Ar values that are representative of the samples’ initial composition.     

Atmospheric and juvenile noble gases in the Skaergaard layered igneous intrusion

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

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

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