Peter H. Barry

Helium isotopes at Rungwe Volcanic Province, Tanzania, and the origin of East African Plateaux

[1]xa0We report helium isotope ratios (3He/4He) of lavas and tephra of the Rungwe Volcanic Province (RVP) in southern Tanzania. Values as high as 15RA (RA = air 3He/4He) far exceed typical upper mantle values, and are the first observation of plume-like ratios south of the Turkana Depression which separates the topographic highs of the Ethiopia and Kenya domes. The African Superplume - a tilted low-velocity seismic anomaly extending to the core-mantle boundary beneath southern Africa – is the likely source of these high 3He/4He ratios. High 3He/4He ratios at RVP together with similarly-high values along the Main Ethiopian Rift and in Afar provide compelling evidence that the African Superplume is a feature that extends through the 670-km seismic discontinuity and provides dynamic support – either as a single plume or via multiple upwellings – for the two main topographic features of the East Africa Rift System as well as heat and mass to drive continuing rift-related magmatism.

Komsomolskaya diamondiferous eclogites: evidence for oceanic crustal protoliths

The Komsomolskaya kimberlite is one of numerous (>1,000) kimberlite pipes that host eclogite xenoliths on the Siberian craton. Eclogite xenoliths from the adjacent Udachnaya kimberlite pipe have previously been geochemically well characterized; however, data from surrounding diamond-bearing kimberlite pipes from the center of the craton are relatively sparse. Here, we report major- and trace-element data, as well as oxygen isotope systematics, for mineral separates of diamondiferous eclogite xenoliths from the Komsomolskaya kimberlite, suggesting two distinct subgroups of a metamorphosed, subducted oceanic crustal protolith. Using almandine contents, this suite can be divided into two subgroups: group B1, with a high almandine component (>20xa0mol%) and group B2, with a low almandine component (<20xa0mol%). Reconstructed REE profiles for B1 eclogites overlap with typical oceanic basalts and lack distinct Eu anomalies. In addition, elevated oxygen isotope values, which are interpreted to reflect isotopic exchange with seawater at low temperatures (<350xa0°C), are consistent with an upper-oceanic crustal protolith. Reconstructed REE profiles for B2 eclogites are consistent with oceanic gabbros and display distinct Eu anomalies, suggesting a plagioclase-rich cumulate protolith. In contrast to B1, B2 eclogites do not display elevated oxygen isotope values, suggesting an origin deep within the crustal pile, where little-to-no interaction with hydrothermal fluids has occurred. Major-element systematics were reconstructed based on mineral modes; group B1 eclogites have higher MgO wt% and lower SiO2 wt%, with respect to typical oceanic basalts, reflecting a partial melting event during slab subduction. Calculated residues from batch partial melt modeling of a range of Precambrian basalts overlap with group B1 trace-element chemistry. When taken together with the respective partial melt trajectories, these melting events are clearly linked to the formation of Tonalite–Trondhjemite–Granodiorite (TTG) complexes. As a result, we propose that many, if not all, diamondiferous eclogite xenoliths from Komsomolskaya represent mantle ‘restites’ that preserve chemical signatures of Precambrian oceanic crust.

Mantle 3He and CO2 degassing in carbonic and geothermal springs of Colorado and implications for neotectonics of the Rocky Mountains

Helium isotope ( 3 He/ 4 He) data from geothermal springs in the Colorado Rocky Mountains (western United States) provide unequivocal evidence for a remarkable mantle-to-groundwater connection, with contributions of up to 27% mantle-derived helium. Hydrochemical modeling of springs shows the mantle helium is associated with high p CO 2 with 76 ± 20% of the CO 2 also derived from endogenic (deep geologic) sources. These springs occur preferentially along faults, have highest 3 He/ 4 He values above domains of low mantle velocity, and demonstrate unexpectedly widespread neotectonic mantle degassing. Total CO 2 flux through these springs is 3 × 10 8 mol/yr, a small but persistent contribution to the CO 2 budget and an important baseline for carbon sequestration/leakage studies.

High precision nitrogen isotope measurements in oceanic basalts using a static triple collection noble gas mass spectrometer

[1]xa0We describe a new system for the simultaneous static triple-collection of nitrogen isotopes at the <10μcm3 STP [N2] (<1 × 10−5 cm3STP; <0.5 nmol) level using a modified VG-5440 noble gas mass spectrometer. The system consists of an internal N2-STD with aδ15N value of −0.11 ± 0.22 ‰ (1σ) calibrated against an air-standard (Air-STD). The N2-STD was measured repeatedly with an average uncertainty on an individualδ15N measurement being 0.03 ‰ (1σ) versus an average single day reproducibility of 0.38 ‰ (1σ). Additional refinements include (1) monitoring of interfering CO contributions at mass 30, allowing a comprehensive CO correction to be applied to all samples, (2) quantification of procedural N2 blanks (n = 22) in both size (4.2 ± 0.5 μcm3 STP) and isotopic composition (δ15N = 12.64 ± 2.04 ‰), allowing consistent blank corrections to all samples, and (3) independent measurement of N2/Ar ratios using a quadrupole mass spectrometer (QMS). The new system was tested by measuring nitrogen isotopes (δ15N), concentrations and N2/Ar ratios on 11 submarine basalt glasses. Results show that the uncertainty on the δ15N data is improved as a consequence of multiple standards being run per day. Reduced analytical times, afforded by triple collection, also minimize sample depletion and memory effects, thus improving measurement statistics. Additionally, we show that CO corrections can be accomplished using mass 30 to monitor CO interferences, leading to substantial improvements in reproducibility and the overall accuracy of results when the contribution of CO is significant.

The secondary origin of diamonds: multi-modal radiation tomography of diamondiferous mantle eclogites

Three-dimensional neutron and X-ray tomography reveals the textural and spatial relationship of diamonds and associated minerals in situ, in a unique suite of 17 diamondiferous eclogites. We emphasize the reporting of X-ray imaging on mantle xenoliths, which in combination with neutron imaging enables the clear identification of diamonds and interstitial metasomatic secondary minerals. In particular, neutrons are highly sensitive to hydrogen (H), allowing for the identification of OH- and H2O-bearing metasomatic minerals. The identification of metasomatic minerals allows for the delineation of distinct metasomatic pathways through the eclogite xenoliths. Diamonds are readily identified as the darkest greyscales due to their low attenuation, and are typically surrounded by secondary minerals, never in contact with primary minerals, and always confined within metasomatic pathways. The ubiquitous occurrence of diamonds in association with pathways suggests a potential genetic link. Both octahedral and dodecahedral diamonds are observed within individual xenoliths, suggesting multiple heterogeneous growth and dissolution processes at small scales. The distinct age dichotomy between eclogite xenoliths and metasomatic mineral assemblages implies that the observed textural relationship of diamonds and late-stage metasomatic pathways for this suite of 17 eclogites casts doubt on the theory that eclogitic diamonds formed billions of years ago. Diamonds are interpreted to have formed from multiple growth episodes, with the last of these episodes represented by the metasomatic assemblages observed in this study. This further indicates that eclogitic diamond inclusions may span large time scales from ancient ages (>2 Ga) all the way to the last growth event, perhaps even close to the time of kimberlite emplacement (~360 Ma), which has significant implications for age-dating of diamonds and the study of diamonds as a whole.

A new syringe pump apparatus for the retrieval and temporal analysis of helium in groundwaters and geothermal fluids

[1]xa0We present details of a newly designed syringe pump apparatus for the retrieval and temporal analysis of helium (SPARTAH). The device is composed of a commercially available syringe pump connected to coils of Cu tubing, which interface the syringe and the groundwater or geothermal wellhead. Through test deployments at geothermal wells in Iceland and California, we show that well fluids are drawn smoothly, accurately, and continuously into the Cu tubing and can be time-stamped through user-determined operating parameters. In the laboratory, the tubing is sectioned to reveal helium (He) characteristics of the fluids at times and for durations of interest. The device is capable of prolonged deployments, up to 6 months or more, with minimal maintenance. It can be used to produce detailed time series records of He, or any other geochemical parameter, in groundwaters and geothermal fluids. SPARTAH has application in monitoring projects assessing the relationship between external transient events (e.g., earthquakes) and geochemical signals in aqueous fluids.

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.

Spatially Variable CO2 Degassing in the Main Ethiopian Rift: Implications for Magma Storage, Volatile Transport, and Rift‐Related Emissions

Deep carbon emissions from historically inactive volcanoes, hydrothermal, and tectonic structures are among the greatest unknowns in the long-term (∼Myr) carbon cycle. Recent estimates of diffuse CO2 flux from the Eastern Rift of the East African Rift System (EARS) suggest this could equal emissions from the entire mid-ocean ridge system. We report new CO2 surveys from the Main Ethiopian Rift (MER, northernmost EARS), and reassess the rift-related CO2 flux. Since degassing in the MER is concentrated in discrete areas of volcanic and off-edifice activity, characterization of such areas is important for extrapolation to a rift-scale budget. Locations of hot springs and fumaroles along the rift show numerous geothermal areas away from volcanic edifices. With these new data, we estimate total CO2 emissions from the central and northern MER as 0.52–4.36 Mtxa0yr−1. Our extrapolated flux from the Eastern Rift is 3.9–32.7 Mtxa0yr−1 CO2, overlapping with lower end of the range presented in recent estimates. By scaling, we suggest that 6–18 Mtxa0yr−1 CO2 flux can be accounted for by magmatic extension, which implies an important role for volatile-enriched lithosphere, crustal assimilation, and/or additional magmatic intrusion to account for the upper range of flux estimates. Our results also have implications for the nature of volcanism in the MER. Many geothermal areas are found >10 km from the nearest volcanic center, suggesting ongoing hazards associated with regional volcanism.

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.