Chris J. Ballentine

Dynamical models of mantle volatile evolution and the role of phase transitions and temperature-dependent rheology

Helium isotopic variations demand the preservation of a primitive volatile source for ocean island basalts (OIB) in conjunction with a well-mixed and more radiogenic source for mid-oceanic ridge basalts (MORB). Dynamical models of the Earths evolution should be able to predict this basic geochemical observation. We have developed a number of increasingly more realistic models of mantle convection that satisfy present-day heat loss and plate velocities to study the eects of convective mixing, radiogenic ingrowth, and degassing on the mantle 3 He/ 4 He evolution. We have included mechanisms that have been proposed to enhance the isolation of individual reservoirs in the mantle such as high lower mantle viscosity, strongly temperature- and pressure-dependent rheology, and an endothermic phase transition at 670 km depth. Although the combination of these mechanisms can produce regions of lower mixing eciency, our models cannot satisfactorily explain the existence of two distinct OIB and MORB 3 He= 4 He sources. If further improvements to the model, such as simulated plates and continents, still fail to explain the geochemical constraints, it may be prudent to consider sources of primitive helium beyond the current paradigm requiring them to be stored within the terrestrial mantle since early in the Earths history.

The contribution of the Precambrian continental lithosphere to global H 2 production

Microbial ecosystems can be sustained by hydrogen gas (H2)-producing water–rock interactions in the Earth’s subsurface and at deep ocean vents. Current estimates of global H2 production from the marine lithosphere by water–rock reactions (hydration) are in the range of 1011xa0moles per year. Recent explorations of saline fracture waters in the Precambrian continental subsurface have identified environments as rich in H2 as hydrothermal vents and seafloor-spreading centres and have suggested a link between dissolved H2 and the radiolytic dissociation of water. However, extrapolation of a regional H2 flux based on the deep gold mines of the Witwatersrand basin in South Africa yields a contribution of the Precambrian lithosphere to global H2 production that was thought to be negligible (0.009xa0×xa01011xa0moles per year). Here we present a global compilation of published and new H2 concentration data obtained from Precambrian rocks and find that the H2 production potential of the Precambrian continental lithosphere has been underestimated. We suggest that this can be explained by a lack of consideration of additional H2-producing reactions, such as serpentinization, and the absence of appropriate scaling of H2 measurements from these environments to account for the fact that Precambrian crust represents over 70 per cent of global continental crust surface area. If H2 production via both radiolysis and hydration reactions is taken into account, our estimate of H2 production rates from the Precambrian continental lithosphere of 0.36–2.27xa0×xa01011xa0moles per year is comparable to estimates from marine systems.

Estimating the recharge properties of the deep ocean using noble gases and helium isotopes

The distribution of noble gases and helium isotopes in the dense shelf waters of Antarctica reflect the boundary conditions near the ocean surface: air-sea exchange, sea ice formation and subsurface ice melt. We use a non-linear least-squares solution to determine the value of the recharge temperature and salinity, as well as the excess air injection and glacial meltwater content throughout the water column and in the precursor to Antarctic Bottom Water. The noble gas-derived recharge temperature and salinity in the Weddell Gyre are -1.95 °C and 34.95 psu near 5500 m; these cold, salty recharge values are a result of surface cooling as well as brine rejection during sea ice formation in Antarctic polynyas. In comparison, the global value for deep water recharge temperature is -0.44 °C at 5500 m, which is 1.5 °C warmer than the southern hemisphere deep water recharge temperature, reflecting the contribution from the north Atlantic. The contrast between northern and southern hemisphere recharge properties highlight the impact of sea ice formation on setting the gas properties in southern sourced deep water. Below 1000 m, glacial meltwater averages 3.5 ‰ by volume and represents greater than 50% of the excess neon and argon found in the water column. These results indicate glacial melt has a non-negligible impact on the atmospheric gas content of Antarctic Bottom Water.

High resolution profile of inorganic aqueous geochemistry and key redox zones in an arsenic bearing aquifer in Cambodia

Arsenic contamination of groundwaters in South and Southeast Asia is a major threat to public health. In order to better understand the geochemical controls on the mobility of arsenic in a heavily arsenic-affected aquifer in northern Kandal Province, Cambodia, key changes in inorganic aqueous geochemistry have been monitored at high vertical and lateral resolution along dominant groundwater flow paths along two distinct transects. The two transects are characterized by differing geochemical, hydrological and lithological conditions. Arsenic concentrations in groundwater are highly heterogenous, and are broadly positively associated with iron and negatively associated with sulfate and dissolved oxygen. The observed correlations are generally consistent with arsenic mobilization by reductive-dissolution of iron (hydr)oxides. Key redox zones, as identified using groupings of the PHREEQC model equilibrium electron activity of major redox couples (notably ammonium/nitrite; ammonium/nitrate; nitrite/nitrate; dissolved oxygen/water) have been identified and vary with depth, site and season. Mineral saturation is also characterized. Seasonal changes in groundwater chemistry were observed in areas which were (i) sandy and of high permeability; (ii) in close proximity to rivers; and/or (iii) in close proximity to ponds. Such changes are attributed to monsoonal-driven surface-groundwater interactions and are consistent with the separate provenance of recharge sources as identified using stable isotope mixing models.

Determining fluid migration and isolation times in multiphase crustal domains using noble gases.

Geochemical characteristics in subsurface fluid systems provide a wealth of information about fluid sources, migration, and storage conditions. Determining the extent of fluid interaction (aquifer-hydrocarbon connectivity) is important for oil and gas production and waste storage applications, but is not tractable using traditional seismic methods. Furthermore, the residence time of fluids is critical in such systems and can vary from tens of thousands to billions of years. Our understanding of the transport length scales in multiphase systems, while equally important, is more limited. Noble gas data from the Rotliegend natural gas field, northern Germany, are used here to determine the length scale and isolation age of the combined water-gas system. We show that geologically bound volume estimates (i.e., gas to water volume ratios) match closed-system noble gas model predictions, suggesting that the Rotliegend system has remained isolated as a closed system since hydrocarbon formation. Radiogenic helium data show that fluid isolation occurred 63–129 m.y. after rock and/or groundwater deposition (ca. 300 Ma), which is consistent with known hydrocarbon generation from 250 to 140 Ma, thus corroborating long-term geologic isolation. It is critical that we have the ability to distinguish between fluid systems that, despite phase separation, have remained closed to fluid loss from those that have lost oil or gas phases. These findings are the first to demonstrate that such systems remain isolated and fully gas retentive on time scales >100 m.y. over >10 km length scales, and have broad implications for saline aquifer CO2 disposal site viability and hydrocarbon resource prediction, which both require an understanding of the length and time scales of crustal fluid transport pathways.

Halogens in chondritic meteorites and terrestrial accretion

Volatile element delivery and retention played a fundamental part in Earth’s formation and subsequent chemical differentiation. The heavy halogens—chlorine (Cl), bromine (Br) and iodine (I)—are key tracers of accretionary processes owing to their high volatility and incompatibility, but have low abundances in most geological and planetary materials. However, noble gas proxy isotopes produced during neutron irradiation provide a high-sensitivity tool for the determination of heavy halogen abundances. Using such isotopes, here we show that Cl, Br and I abundances in carbonaceous, enstatite, Rumuruti and primitive ordinary chondrites are about 6 times, 9 times and 15–37 times lower, respectively, than previously reported and usually accepted estimates. This is independent of the oxidation state or petrological type of the chondrites. The ratios Br/Cl and I/Cl in all studied chondrites show a limited range, indistinguishable from bulk silicate Earth estimates. Our results demonstrate that the halogen depletion of bulk silicate Earth relative to primitive meteorites is consistent with the depletion of lithophile elements of similar volatility. These results for carbonaceous chondrites reveal that late accretion, constrained to a maximum of 0.5u2009±u20090.2 per cent of Earth’s silicate mass, cannot solely account for present-day terrestrial halogen inventories. It is estimated that 80–90 per cent of heavy halogens are concentrated in Earth’s surface reservoirs and have not undergone the extreme early loss observed in atmosphere-forming elements. Therefore, in addition to late-stage terrestrial accretion of halogens and mantle degassing, which has removed less than half of Earth’s dissolved mantle gases, the efficient extraction of halogen-rich fluids from the solid Earth during the earliest stages of terrestrial differentiation is also required to explain the presence of these heavy halogens at the surface. The hydropilic nature of halogens, whereby they track with water, supports this requirement, and is consistent with volatile-rich or water-rich late-stage terrestrial accretion.

End-Permian extinction amplified by plume-induced release of recycled lithospheric volatiles

Magmatic volatile release to the atmosphere can lead to climatic changes and substantial environmental degradation including the production of acid rain, ocean acidification and ozone depletion, potentially resulting in the collapse of the biosphere. The largest recorded mass extinction in Earth’s history occurred at the end of the Permian, coinciding with the emplacement of the Siberian large igneous province, suggesting that large-scale magmatism is a key driver of global environmental change. However, the source and nature of volatiles in the Siberian large igneous province remain contentious. Here we present halogen compositions of sub-continental lithospheric mantle xenoliths emplaced before and after the eruption of the Siberian flood basalts. We show that the Siberian lithosphere is massively enriched in halogens from the infiltration of subducted seawater-derived volatiles and that a considerable amount (up to 70%) of lithospheric halogens are assimilated into the plume and released to the atmosphere during emplacement. Plume–lithosphere interaction is therefore a key process controlling the volatile content of large igneous provinces and thus the extent of environmental crises, leading to mass extinctions during their emplacement.Halogens in Siberian xenoliths show that plume–lithosphere interaction controls the volatile content of large igneous provinces. The seawater-derived volatiles, implicated in the end-Permian mass extinction, infiltrated the lithosphere during subduction.

Author Correction: End-Permian extinction amplified by plume-induced release of recycled lithospheric volatiles

In the version of this Article originally published, refs 28–31 were listed in the wrong order, resulting in the citations in the main text being incorrect. The citations and reference list have now been updated in the online versions; the corrected order is shown below.

Effect of water on the fluorine and chlorine partitioning behavior between olivine and silicate melt

Halogens show a range from moderate (F) to highly (Cl, Br, I) volatile and incompatible behavior, which makes them excellent tracers for volatile transport processes in the Earth’s mantle. Experimentally determined fluorine and chlorine partitioning data between mantle minerals and silicate melt enable us to estimate Mid Ocean Ridge Basalt (MORB) and Ocean Island Basalt (OIB) source region concentrations for these elements. This study investigates the effect of varying small amounts of water on the fluorine and chlorine partitioning behavior at 1280u2009°C and 0.3 GPa between olivine and silicate melt in the Fe-free CMAS+F–Cl–Br–I–H2O model system. Results show that, within the uncertainty of the analyses, water has no effect on the chlorine partitioning behavior for bulk water contents ranging from 0.03 (2) wt% H2O (DClol/melt = 1.6u2009±u20090.9xa0×xa010−4) to 0.33 (6) wt% H2O (DClol/melt = 2.2u2009±u20091.1 × 10−4). Consequently, with the effect of pressure being negligible in the uppermost mantle (Joachim et al. Chem Geol 416:65–78, 2015), temperature is the only parameter that needs to be considered for the determination of chlorine partition coefficients between olivine and melt at least in the simplified iron-free CMAS+F–Cl–Br–I–H2O system. In contrast, the fluorine partition coefficient increases linearly in this range and may be described at 1280u2009°C and 0.3 GPa with (R2u2009=u20090.99):