Primary N2-He gas field formation in intracratonic sedimentary basins.

Helium, nitrogen and hydrogen are continually generated within the deep continental crust1-9. Conceptual degassing models for quiescent continental crust are dominated by an assumption that these gases are dissolved in water, and that vertical transport in shallower sedimentary systems is by diffusion within water-filled pore space (for example, refs. 7,8). Gas-phase exsolution is crucial for concentrating helium and forming a societal resource. Here we show that crustal nitrogen from the crystalline basement alone-degassing at a steady state in proportion to crustal helium-4 generation-can reach sufficient concentrations at the base of some sedimentary basins to form a free gas phase. Using a gas diffusion model coupled with sedimentary basin evolution, we demonstrate, using a classic intracratonic sedimentary basin (Williston Basin, North America), that crustal nitrogen reaches saturation and forms a gas phase; in this basin, as early as about 140 million years ago. Helium partitions into this gas phase. This gas formation mechanism accounts for the observed primary nitrogen-helium gas discovered in the basal sedimentary lithology of this and other basins, predicts co-occurrence of crustal gas-phase hydrogen, and reduces the flux of helium into overlying strata by about 30 per cent because of phase solubility buffering. Identification of this gas phase formation mechanism provides a quantitative insight to assess the helium and hydrogen resource potential in similar intracontinental sedimentary basins found worldwide.

Temporal variation of planetary iron as a driver of evolution.

Iron is an irreplaceable component of proteins and enzyme systems required for life. This need for iron is a well-characterized evolutionary mechanism for genetic selection. However, there is limited consideration of how iron bioavailability, initially determined by planetary accretion but fluctuating considerably at global scale over geological time frames, has shaped the biosphere. We describe influences of iron on planetary habitability from formation events >4 Gya and initiation of biochemistry from geochemistry through oxygenation of the atmosphere to current host-pathogen dynamics. By determining the iron and transition element distribution within the terrestrial planets, planetary core formation is a constraint on both the crustal composition and the longevity of surface water, hence a planet's habitability. As such, stellar compositions, combined with metallic core-mass fraction, may be an observable characteristic of exoplanets that relates to their ability to support life. On Earth, the stepwise rise of atmospheric oxygen effectively removed gigatons of soluble ferrous iron from habitats, generating evolutionary pressures. Phagocytic, infectious, and symbiotic behaviors, dating from around the Great Oxygenation Event, refocused iron acquisition onto biotic sources, while eukaryotic multicellularity allows iron recycling within an organism. These developments allow life to more efficiently utilize a scarce but vital nutrient. Initiation of terrestrial life benefitted from the biochemical properties of abundant mantle/crustal iron, but the subsequent loss of iron bioavailability may have been an equally important driver of compensatory diversity. This latter concept may have relevance for the predicted future increase in iron deficiency across the food chain caused by elevated atmospheric CO2.

Occurrence and Sources of Radium in Groundwater Associated with Oil Fields in the Southern San Joaquin Valley, California.

Geochemical data from 40 water wells were used to examine the occurrence and sources of radium (Ra) in groundwater associated with three oil fields in California (Fruitvale, Lost Hills, South Belridge). 226Ra+228Ra activities (range = 0.010-0.51 Bq/L) exceeded the 0.185 Bq/L drinking-water standard in 18% of the wells (not drinking-water wells). Radium activities were correlated with TDS concentrations (p < 0.001, ρ = 0.90, range = 145-15,900 mg/L), Mn + Fe concentrations (p < 0.001, ρ = 0.82, range = <0.005-18.5 mg/L), and pH (p < 0.001, ρ = -0.67, range = 6.2-9.2), indicating Ra in groundwater was influenced by salinity, redox, and pH. Ra-rich groundwater was mixed with up to 45% oil-field water at some locations, primarily infiltrating through unlined disposal ponds, based on Cl, Li, noble-gas, and other data. Yet 228Ra/226Ra ratios in pond-impacted groundwater (median = 3.1) differed from those in oil-field water (median = 0.51). PHREEQC mixing calculations and spatial geochemical variations suggest that the Ra in the oil-field water was removed by coprecipitation with secondary barite and adsorption on Mn-Fe precipitates in the near-pond environment. The saline, organic-rich oil-field water subsequently mobilized Ra from downgradient aquifer sediments via Ra-desorption and Mn/Fe-reduction processes. This study demonstrates that infiltration of oil-field water may leach Ra into groundwater by changing salinity and redox conditions in the subsurface rather than by mixing with a high-Ra source.

Solubility trapping in formation water as dominant CO(2) sink in natural gas fields.

Injecting CO(2) into deep geological strata is proposed as a safe and economically favourable means of storing CO(2) captured from industrial point sources. It is difficult, however, to assess the long-term consequences of CO(2) flooding in the subsurface from decadal observations of existing disposal sites. Both the site design and long-term safety modelling critically depend on how and where CO(2) will be stored in the site over its lifetime. Within a geological storage site, the injected CO(2) can dissolve in solution or precipitate as carbonate minerals. Here we identify and quantify the principal mechanism of CO(2) fluid phase removal in nine natural gas fields in North America, China and Europe, using noble gas and carbon isotope tracers. The natural gas fields investigated in our study are dominated by a CO(2) phase and provide a natural analogue for assessing the geological storage of anthropogenic CO(2) over millennial timescales. We find that in seven gas fields with siliciclastic or carbonate-dominated reservoir lithologies, dissolution in formation water at a pH of 5-5.8 is the sole major sink for CO(2). In two fields with siliciclastic reservoir lithologies, some CO(2) loss through precipitation as carbonate minerals cannot be ruled out, but can account for a maximum of 18 per cent of the loss of emplaced CO(2). In view of our findings that geological mineral fixation is a minor CO(2) trapping mechanism in natural gas fields, we suggest that long-term anthropogenic CO(2) storage models in similar geological systems should focus on the potential mobility of CO(2) dissolved in water.

Seawater subduction controls the heavy noble gas composition of the mantle.

The relationship between solar volatiles and those now in the Earth's atmosphere and mantle reservoirs provides insight into the processes controlling the acquisition of volatiles during planetary accretion and their subsequent evolution. Whereas the light noble gases (helium and neon) in the Earth's mantle preserve a solar-like isotopic composition, heavy noble gases (argon, krypton and xenon) have an isotopic composition very similar to that of the modern atmosphere, with radiogenic and (in the case of xenon) solar contributions. Mantle noble gases in a magmatic CO2 natural gas field have been previously corrected for shallow atmosphere/groundwater and crustal additions. Here we analyse new data from this field and show that the elemental composition of non-radiogenic heavy noble gases in the mantle is remarkably similar to that of sea water. We challenge the popular concept of a noble gas 'subduction barrier'--the convecting mantle noble gas isotopic and elemental composition is explained by subduction of sediment and seawater-dominated pore fluids. This accounts for approximately 100% of the non-radiogenic argon and krypton and 80% of the xenon. Approximately 50% of the convecting mantle water concentration can then be explained by this mechanism. Enhanced recycling of subducted material to the mantle plume source region then accounts for the lower ratio of radiogenic to non-radiogenic heavy noble gas isotopes and higher water content of plume-derived basalts.

Neon isotopes constrain convection and volatile origin in the Earth's mantle.

Identifying the origin of primordial volatiles in the Earth's mantle provides a critical test between models that advocate magma-ocean equilibration with an early massive solar-nebula atmosphere and those that require subduction of volatiles implanted in late accreting material. Here we show that neon isotopes in the convecting mantle, resolved in magmatic CO2 well gases, are consistent with a volatile source related to solar corpuscular irradiation of accreting material. This contrasts with recent results that indicated a solar-nebula origin for neon in mantle plume material, which is thought to be sampling the deep mantle. Neon isotope heterogeneity in different mantle sources suggests that models in which the plume source supplies the convecting mantle with its volatile inventory require revision. Although higher than accepted noble gas concentrations in the convecting mantle may reduce the need for a deep mantle volatile flux, any such flux must be dominated by the neon (and helium) isotopic signature of late accreting material.

Recycled Components in Mantle Plumes Deduced From Variations in Halogens (Cl, Br, and I), Trace Elements, and 3He/4He Along the Hawaiian-Emperor Seamount Chain.

Halogens are primarily located within surface reservoirs of the Earth; as such they have proven to be effective tracers for the identification of subducted volatiles within the mantle. Subducting lithologies exhibit a wide variety of halogen compositions, yet the mantle maintains a fairly uniform signature, suggesting halogens may be homogenized during subduction to the mantle or during eruption. Here we present halogen (Cl, Br, and I), K, noble gas, and major and trace element data on olivines from three seamounts along the Hawaiian-Emperor seamount chain to determine if the deep mantle source has retained evidence of halogen heterogeneities introduced through subduction. High Ni contents indicate that the Hawaiian-Emperor mantle source contains a recycled oceanic crust component in the form of pyroxenite, which increases from the 46% in the oldest (Detroit) to 70% in the younger seamount (Koko). Detroit seamount retains mid-ocean ridge basalts (MORB)-like Br/Cl and I/Cl, while the Br/Cl and I/Cl of Suiko and Koko seamounts are higher than MORB and similar to altered oceanic crust and dehydrated serpentinite. Helium isotopes show a similar evolution, from MORB-like values at Detroit seamount toward higher values at Suiko and Koko seamounts. The correlation between pyroxenite contributions, Br/Cl, I/Cl, and 3He/4He indicates that subducted material has been incorporated into the primordial undegassed Hawaiian mantle plume source. The identification of recycled oceanic crustal signatures in both the trace elements and halogens indicates that subduction and dehydration of altered oceanic crust may exert control on the cycling of volatile elements to the deep mantle.

Optimizing Noble Gas-Water Interactions via Monte Carlo Simulations.

In this work we present optimized noble gas-water Lennard-Jones 6-12 pair potentials for each noble gas. Given the significantly different atomic nature of water and the noble gases, the standard Lorentz-Berthelot mixing rules produce inaccurate unlike molecular interactions between these two species. Consequently, we find simulated Henry's coefficients deviate significantly from their experimental counterparts for the investigated thermodynamic range (293-353 K at 1 and 10 atm), due to a poor unlike potential well term (εij). Where εij is too high or low, so too is the strength of the resultant noble gas-water interaction. This observed inadequacy in using the Lorentz-Berthelot mixing rules is countered in this work by scaling εij for helium, neon, argon, and krypton by factors of 0.91, 0.8, 1.1, and 1.05, respectively, to reach a much improved agreement with experimental Henry's coefficients. Due to the highly sensitive nature of the xenon εij term, coupled with the reasonable agreement of the initial values, no scaling factor is applied for this noble gas. These resulting optimized pair potentials also accurately predict partitioning within a CO2-H2O binary phase system as well as diffusion coefficients in ambient water. This further supports the quality of these interaction potentials. Consequently, they can now form a well-grounded basis for the future molecular modeling of multiphase geological systems.

Meteorite Kr in Earth's mantle suggests a late accretionary source for the atmosphere.

Noble gas isotopes are key tracers of both the origin of volatiles found within planets and the processes that control their eventual distribution between planetary interiors and atmospheres. Here, we report the discovery of primordial Kr in samples derived from Earth's mantle and show it to be consistent with a meteorite or fractionated solar nebula source. The high-precision Kr and Xe isotope data together suggest that Earth's interior acquired its volatiles from accretionary material similar to average carbonaceous chondrites and that the noble gases in Earth's atmosphere and oceans are dominantly derived from later volatile capture rather than impact degassing or outgassing of the solid Earth during its main accretionary stage.

What CO2 well gases tell us about the origin of noble gases in the mantle and their relationship to the atmosphere.

Study of commercially produced volcanic CO2 gas associated with the Colorado Plateau, USA, has revealed substantial new information about the noble gas isotopic composition and elemental abundance pattern of the mantle. Combined with published data from mid-ocean ridge basalts, it is now clear that the convecting mantle has a maximum (20)Ne/(22)Ne isotopic composition, indistinguishable from that attributed to solar wind-implanted (SWI) neon in meteorites. This is distinct from the higher (20)Ne/(22)Ne isotopic value expected for solar nebula gases. The non-radiogenic xenon isotopic composition of the well gases shows that 20 per cent of the mantle Xe is 'solar-like' in origin, but cannot resolve the small isotopic difference between the trapped meteorite 'Q'-component and solar Xe. The mantle primordial (20)Ne/(132)Xe is approximately 1400 and is comparable with the upper end of that observed in meteorites. Previous work using the terrestrial (129)I - (129)Xe mass balance demands that almost 99 per cent of the Xe (and therefore other noble gases) has been lost from the accreting solids and that Pu-I closure age models have shown this to have occurred in the first ca 100Ma of the Earth's history. The highest concentrations of Q-Xe and solar wind-implanted (SWI)-Ne measured in meteorites allow for this loss and these high-abundance samples have a Ne/Xe ratio range compatible with the 'recycled-air-corrected' terrestrial mantle. These observations do not support models in which the terrestrial mantle acquired its volatiles from the primary capture of solar nebula gases and, in turn, strongly suggest that the primary terrestrial atmosphere, before isotopic fractionation, is most probably derived from degassed trapped volatiles in accreting material.By contrast, the non-radiogenic argon, krypton and 80 per cent of the xenon in the convecting mantle have the same isotopic composition and elemental abundance pattern as that found in seawater with a small sedimentary Kr and Xe admix. These mantle heavy noble gases are dominated by recycling of air dissolved in seawater back into the mantle. Numerical simulations suggest that plumes sampling the core-mantle boundary would be enriched in seawater-derived noble gases compared with the convecting mantle, and therefore have substantially lower (40)Ar/(36)Ar. This is compatible with observation. The subduction process is not a complete barrier to volatile return to the mantle.

Numerical models, geochemistry and the zero-paradox noble-gas mantle.

Numerical models of whole-mantle convection demonstrate that degassing of the mantle is an inefficient process, resulting in ca. 50% of the (40)Ar being degassed from the mantle system. In this sense the numerical simulations are consistent with the (40)Ar mass balance between the atmosphere and mantle reservoir. These models, however, are unable to preserve the large-scale heterogeneity predicted by models invoking geochemical layering of the mantle system. We show that the three most important noble-gas constraints on the geochemically layered mantle are entirely dependent on the (3)He concentration of the convecting mantle derived from the (3)He flux into the oceans and the average ocean-crust generation rate. A factor of 3.5 increase in the convecting-mantle noble-gas concentration removes all requirements for: a (3)He flux into the upper mantle from a deeper high (3)He source; a boundary in the mantle capable of separating heat from helium; and a substantial deep-mantle reservoir to contain a hidden (40)Ar rich reservoir. We call this model concentration for the convecting mantle the 'zero-paradox' concentration. The time-integrated flux of (3)He into the oceans is a robust observation, but only representative of the ocean-floor activity over the last 1000 years. In contrast, ocean-floor generation occurs over tens of millions of years. We argue that combining these two observations to obtain the (3)He concentration of the mantle beneath mid-ocean ridges is unsound. Other indicators of mantle (3)He concentration suggest that the real value may be at least a factor of two higher. As the zero-paradox concentration is approached, the noble-gas requirement for mantle layering is removed. We further consider the role that recycled material plays in ocean-island-basalt generation and show that a source with high (3)He and (3)He/(4)He must exist within the mantle. Nevertheless, only a small amount of this material is required to generate both the observed ocean-island (3)He/(4)He ratios and the concentrations inferred from basalt samples for this mantle source.