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Because of its remarkable versatility, isotope chemistry is a naturally invasive discipline that has expanded into numerous fields of Earth and planetary sciences, forensics, archeology, biology, and more recently, medical research.

The research done in my group is equally diverse ranging from the study of earliest solids in the Solar System, to deep-sea corals and human civilization vestiges. You can explore these topics in more details below.

Uranium geo- and cosmochemistry

Long-assumed to be constant across all solar system materials, the ratio of the two long-lived isotopes of uranium (238U/235U) varies significantly at the permil and sub-permit level. Understanding the origin of these variations is an important part of my work with applications to early Solar System research, ocean paleoredox reconstructions, magmatic processes and geochronology.

I. The chase for Curium-247

How to turn iron into gold is not just the Magmum Opus of alchemists, but also an important question for astrophysicists and cosmochemists, who are trying to understand the r-process (rapid neutron capture process) of nucleosynthesis. Because some r-nuclides are radioactive, their abundance in the early Solar System (SS) provides a measure of the time interval between their synthesis in stars and the formation of the Solar System itself. This, in turn, provides important insights into the frequency of r-process events and thus, the astrophysical site of the r-process.

Amongst the short-lived r-nuclides with long enough half-lives to be potentially present in the nascent SS, Curium-247 (which decays into 235U, t1/2 = 15.6 Myr) is the only one whose abundance could shed light on the hypothesized existence of an actinide specific r-process site. Yet, despite decades of studies, the abundance (and even the presence) of Curium-247 in the early SS remained intensely debated, leading Gerry Wasserburg to say “ 247Cm occurred abundantly in a journal called Nature, but did not occur in nature.“

Relevant publications:

Slab of the Allende meteorite showing refractory inclusions (left), and Early Solar System abundances vs mean life of short-lived radionuclide showing a similar isolation time from the interstellar medium for r-process elements (~100 Myr, right).

Tissot et al. (2016) — An analytical tour-de-force reporting the U isotope composition of refractory inclusions (oldest known SS solids), including Curious Marie: an extremely U-depleted inclusion, with a 235U excess of 59 ‰􏰁. These data brought definitive evidence that 247Cm was alive in the early solar nebula, and demonstrated that intermediate and high mass r-nuclides are presumably produced in the same site for most of the history of the Galaxy.

Tang et al. (2017) — A detailed followed up study using in-situ techniques (26Al-26Mg, 36Cl-36S) to constrain the formation and alteration ages of Curious Marie. The early alteration responsible for Cm/U fractionation allows up to decrease by a factor 5 the uncertainty on the initial 247cm abundance in the early SS. This work also provides evidence for the coexistence of 26Al and 36Cl in the early solar nebula, raising the possibility that, in addition to an irradiation origin, 36Cl could have also been derived from a stellar source.

Expectations for different type of alteration that a refractory inclusion could experience.

 

II. The U paleoredox proxy

Pioneering studies from the mid-2000s found that amongst sedimentary archives, reduced sediments (e.g., black shales) were enriched by up to 1.2 ‰ relative to ambient seawater. Since then, 238U/235U variations in marine sediments (predominantly carbonates) has become, arguably, the most widely-used proxy of ocean paleoredox conditions.

Since my Ph.D., and now with my group, I have been working on various aspects of the proxy, including (i) validating its status as a tracer of global oceanic redox conditions, (ii) examining its sensitivity to diagenesis in carbonates, and (iii) developing quantitative tools to robustly interpret past signals preserved in the sedimentary record.

Relevant publications:

Correction for detrital contamination.

 

Asael et al. (2013) — A multi-proxy stable isotope (Mo, Fe, U) case-study of shales from the upper Zaonega Formation (2.06 Ga, Fennoscandia) aiming to understand the evolving ocean redox conditions in the wake of the Great Oxidation Event. This study highlights the caveat of detrital correction for U paleo redox reconstructions using shales.

 

Tissot & Dauphas (2015) — Details the methods for high-precision measurement of U by double spike technique and introduces an error propagation tool using MonteCarlo simulations. This paper then carefully examines the composition of the crust, and establishes the mass and isotope budget of the modern ocean. It demonstrates that U isotopes do indeed act as tracer of global oceanic redox conditions.

Oxidative weathering mobilizes U from the crust to the ocean, which is then removed into sedimentary sinks: predominantly carbonates, suboxic, and anoxic sediments.

Sea-level stand exerts a strong control on the δ238U record through mixing of platform-derived carbonates (~0.50–0.60‰ heavier than seawater) and pelagic carbonates (with seawater-like δ238U values).

Tissot et al. (2018) — We introduce a simple step-leaching protocol for bulk carbonate δ238U analysis, and apply it to 43 shallow-water carbonates from the Bahamas Platform (ODP Leg 166 Site 1009). The samples, formed in oxygenated waters over the last 1.5 Myr, show large down-core δ238U variations suggesting a strong eustatic control on 238U/235U. This study emphasizes the need for statistically meaningful data sets and proper consideration of the depositional environment for paleoredox reconstructions using the carbonate record.

 

Bonus: As the method also provides high-precision on 234U/238U ratios, the data also confirmed the existence of cyclical variations in seawater (234U/238U) over, at least, the last 2 glacial-interglacial events (0.23 Myr), which has implications for screening U-Th ages of carbonates.

Small-scale (1–15‰) variations in seawater (234U/238U) mirror sea-level changes during the last two glacial-interglacial periods.

Many Archean and Proterozoic carbonates have unfractionated δ238U values similar to those of continents and riverine runoff, raising questions about (1) U residence time in the ancient ocean, and/or (2) the constancy of the seawater-anoxic sediment isotope fractionation factor.

 

Chen et al. (2021) — A study of the δ238U secular trends in carbonates and shales over the geologic record. This study explores the relationship between extent of marine anoxia and U residence time, and highlights the challenges inherent to applying knowledge of the modern marine U isotopic cycle to periods of Earth’s history when ocean-floor anoxia was much more extensive, and atmospheric oxygen content was significantly lower than present.

Kipp & Tissot (2022) — This contributions highlights the limitations and pitfalls of steady-state calculations or illustrative forward modeling to constrain past oceanic anoxia during transient or short lived (< 5 Myr) events, or when anoxia is widespread (as the proxy loses its sensitivity). This paper then introduces an inverse (Bayesian inference) modeling approach that enables robust quantification of seafloor anoxia within and amongst δ238U datasets. (See Download page for code).

Workflow of the Markov Chain Monte Carlo routine used for robust seafloor anoxia quantification.

 

III. U isotopes in magmatic environments

Extensively studied in the context of oceanic paleoredox reconstructions and ore deposit formation, the U isotope system is also garnering attention in igneous samples for its potential as a tracer of Soret (thermal) diffusion, subduction and sediment recycling, or for the impact that 238U/235U variations have on U-Pb and Pb-Pb ages.

Relevant publications:

The data do not follow the correlation expected for Soret diffusion.

 

Telus et al. (2012) — Multi-isotope (Fe, Zn, Mg, U) case-study of differentiated crustal rocks, including I- (igneous), and S-type (sedimentary) granites from the Lachlan Fold Belt (Australia). The nature and redox state of the protolith do not appear to influence the δ238U compositions of granitic rocks. The lack of a positive correlation between the δ26Mg, δ238U and δ56Fe rules out Soret diffusion as the origin of isotope variations in the studied systems.

 

Tissot & Dauphas (2015) — In this paper, new data on igneous samples and a thorough literature compilation are combined to carefully examine the U isotope composition of the crust.

Igneous rocks show as much variability as some sedimentary archives.

Dichotomy in the 238U/235U of angrites.

 

Tissot et al. (2017) — We report the discovery of distinct δ238U and REE patterns between quenched (rapidly cooled) and plutonic (slowly cooled) angrites. This is best explained as the result of magmatic differentiation, providing evidence for U stable isotope fractionation during magmatic processes.

Tissot et al. (2019) — The first report of high-precision δ238U in single-zircon grains (previous studies pooled 100s to 1000s of grain for an analysis). We show that single-zircon δ238U measurements are not only possible but also broadly applicable, and could enable (i) improvements in precision/accuracy of U–Pb and Pb–Pb dates, (ii) accurate investigation of U-series disequilibrium contribution to U–Pb discordance, and (iii) accurate re-evaluation of U decay constants. Data on Hadean/Archean grains argues against the widespread existence of natural nuclear reactors (Oklo-like) in the early Earth.

Single-grain analysis of Jack Hills zircon show very limited variability.

MC-ICP-MS instruments have led to the rapid expansion of U isotope investigations in numerous fields.

 

Tissot & Ibañez-Mejia (2021) — A review article highlighting the striking features of the δ238U record of igneous rocks and minerals, and discussing the type of key multi-disciplinary investigations that are need to establish a robust interpretative framework for δ238U variations in igneous systems. We pose the question: could we turn these currently enigmatic U isotope variations into reliable probes of high-T processes?


Angrites petrogenesis

Angrites are differentiated meteorites that have acquired an important status in Early Solar System (ESS) research owing to (i) their extreme volatile element, (ii) their early formation ages, (iii) and their (partial) isotopic similarity with the Earth and Mars. Understanding the accretion and evolution history of angrites can therefore illuminate the processes that shaped the inner SS in general, including the Earth and the terrestrial planets.

Relevant publications:

Tissot et al. (2017) — 238U/235U variations impact the accuracy of Pb-Pb ages. This paper present high-precision U isotope data, accordingly corrects the Pb-Pb ages of angrites, and revisits the agreement between the relative chronologies inferred from short-lived radionuclides (26Al, 53Mn, 182Hf) and the absolute Pb-Pb clock. The discovery of distinct δ238U and REE patterns between quenched (rapidly cooled) and plutonic (slowly cooled) angrites is best explained as the result of magmatic differentiation, providing evidence for U stable isotope fractionation during magmatic processes.

Angrites with fractionated REE patterns also show lower than average Solar System δ238U values.

Our pressure experiments indicate that the angrite parent body had a radius of at least ~600–770 km (about 3x larger than Vesta, the parent body of HED meteorites).

Tissot et al. (2022) — A petrogenetic study of angrites, leveraging the rapidly growing number of known specimens (> 5x over 20 years). We find that volcanic angrites define two compositional groups readily related by fractional crystallization. Pressure experiments indicate that the parental melt of the evolved lavas last equilibrated at 6-9 bar, requiring a minimum radius for the angrite parent body (APB) of 600-700 km. Using the composition of the more primitive lavas we derived a self-consistent estimate of the major elements abundances in the APB, which suggest that the volatile-depleted nature of the APB is a primitive feature resulting from nebular fractionation at high-T (~1300–1400 K). We make the case that the APB represents the archetype of the first-generation of refractory-enriched planetesimals and embryos formed in the innermost part of the inner Solar System (<1 AU), and which accreted in the telluric planets.

Research supported by a W.O. Crosby postdoctoral fellowship (01/2016 to 12/2017), a David and Lucille Packard Fellowship, and start-up funds provided by Caltech.


Early Solar System

The elemental and isotopic composition of planets and meteorites (and their inclusions) records a long succession of processes from nucleosynthesis to planetary differentiation. The corrollary is that we can study the events that shaped our Solar System, through the characterization of the elemental and isotopic composition of planets and meteorites. When trying to unravel the composition and architecture of the nascent solar nebula, we focus on the oldest known solids formed in the solar system: Calcium, Aluminum-rich inclusions (or CAIs).

Relevant publications:

 

Davis et al. (2018) — A study of titanium isotopes and Rare Earth Element (REE) pattern in texturally diverse CAIs from Allende. The correlated Ti isotope anomalies point to contributions from at least two sources, likely Type II supernovae for 46Ti and Type Ia or electron-capture supernovae for 50Ti. The finding that the CAIs with the highest ε50Ti anomalies also show more dispersion in their mass-dependent δ49Ti suggests that thermal processing (evaporation/condensation) and gas-dust decoupling may have been responsible for the presence of titanium isotope anomalies in CAIs and bulk meteorites of different groups.

There is no correlation between mass dependent (δ49Ti) and independent (ε50Ti) effects in Ti in CAIs, but there tends to be a greater spread in δ49Ti at higher ε50Ti.

Ti and Sr isotope anomalies in CAIs (blue/red) and planetary materials (yellow). While CAIs account for at most a 3-5% (vol) of chondrites, they have similar 84Sr enrichments, pointing to the control of the Sr inventory of carbonaceous chondrites of a yet-unidentified cryptic refractory dust (CRD).

Charlier et al. (2019) — The first combined nucleosynthetic, radiogenic and stable strontium isotope characterization of fine- and coarse-grained CAIs (using inclusions from Allende). All CAIs, regardless of texture, show apparent enrichment in 84Sr with variability far outside analytical uncertainties, testifying to some degree of heterogeneity in the CAI forming region. The similar magnitude of 84Sr excess in CAIs and carbonaceous chondrites, suggests that the inventories of Sr (and other refractory elements) in carbonaceous chondrites are dominated by a cryptic refractory dust component (CRD) that was formed early and near the Sun, and was subsequently transported outwards to the carbonaceous chondrite-forming region.

Pravdivsteva et al. (2020) — A step-pyrolysis study of noble gases in the Curious Marie CAI revealing the preservation of an s-process carrier in CAIs. This contrasts with the commonly held view that presolar grains are found solely in the fine-grained rims surrounding chondrules and in the low-temperature fine-grained matrix that binds the various meteoritic components together. The noble gases signatures are most consistent with SiC grains as the carriers. This study provides the first evidence that premolar grains were incorporated into fine-grained CAIs in the Allende carbonaceous chondrite at the time of their formation, and have survived parent-body processing.

The Xe-G (s-process) component, clearly contributes to the CAIs’ Xe budget, requiring an s-process carrier to be present in the sample and thermal destroyed at ~1250°C.

Schematic of two-stage model needed to explain the REE patterns and isotopic compositions of typical group II CAIs.

Hu et al. (2021) — The first investigation of mass-dependent isotope effects of all multi-isotopic REEs in CAIs. (from Allende). The light isotope enrichment of the most refractory REEs and more subdued isotopic variations of the least refractory REEs argue against group II CAIs as product of equilibration condensation. Instead, a two-stage process involving fast evaporation of preexisting materials, followed by near-equilibrium recondensation is needed, possibly in events akin to FU Orionis– or EX Lupi–type outbursts of eruptive pre–main-sequence stars.

 

Charlier et al. (2021) — A step-leaching study of nine unmelted CAIs from Allende. The chemically resistant residues show extreme positive μ84Sr (up to +80,655) and 87Sr variations that cannot be explained by decay of 87Rb, pointing to the presence in fine-grained CAIs of a presolar carrier enriched in the p-nuclide (84Sr). We argue that this unidentified carrier controls the isotopic anomalies in bulk CAIs and outer solar system materials, which reinstates the chronological signif- icance of differences in initial 87Sr/86Sr between CAIs and volatile-depleted inner solar system materials.

A pure 84Sr component is required to explained the percent-level excesses observed in the most refractory fractions (L5) of fine-grained CAIs.

 

Research supported by a W.O. Crosby postdoctoral fellowship (01/2016 to 12/2017), and start-up funds provided by Caltech.


Zirconium isotopes research 

Zirconium is a commonly used elemental tracer of silicate differentiation, yet its stable isotope systematics remain poorly known. Along with collaborator Mauricio Ibañez-Mejia (U. of Arizona) we have developed analytical routines to determine the Zr stable isotope composition of single minerals and bulk-rock samples using a new 91Zr-96Zr double-spike. These capabilities are being used to explore the Zr isotopic systematics of various geochemical reservoirs on Earth, their variability, and the petrologic processes responsible for the observed fractionations.

Relevant publications:

Zr purification protocol for zircon and baddeleyite.

 

Tompkins et al. (2020) — Details the analytical methods for Zr isotopic analysis of zircon and introduces the MTUR1 zircon standard for in-situ δ94/90Zr work.

Ibañez-Mejia & Tisot (2019) — Pioneering study showing that Zr-rich phases (i.e., zircon, baddeleyite) from the FC-1 gabbros of the Duluth Complex exhibit δ94/90Zr variability in excess of 5 ‰! These observations suggest that Zr stable isotopes in zircon may provide a powerful new tracer of magmatic differentiation and a means to probe the history of Zr removal from magmatic liquids during fractional crystallization.

Extreme variations in δ94/90Zr are observed in the Duluth Gabbro.

For many of the systems studied, equilibrium mass-dependent effects do not seem to be the main driver of Zr isotope fractionation.

 

Méheut et al. (2021) — Results from ab initio calculations showing that equilibrium Zr isotope effects are negligible at magmatic temperatures (Δ94/90Zr <0.05 ‰ between zircon and melt at > 700C). The extreme fractionations observed in zircon from the Duluth Gabbro (previous paper), can be explained instead as the result of kinetic isotopic fractionation effects within the diffusive boundary layers that develop in crystallizing magmas.

Research supported by NSF-EAR grants 1823748 (to Ibañez-Mejia) and 1824002 (to Tissot). Duration: 09/2018 to 09/2021.