Konstantin Ignatyev

Metal–organic frameworks (MOFs) hold immense potential for applications from separations to catalysis, yet their long-term behaviour across real-world environments remains unclear. Here we introduce a hierarchical exposure framework that tracks the structural and chemical transformations in the archetypal zirconium MOF UiO-66 across sequential compartments - atmospheric gases, air, aqueous media and a biological host – and resolves how prior exposures condition or prime subsequent transformations. Using synchrotron-based spectroscopy, we find that oxidative gases leave the Zr-carboxylate nodes essentially intact, whereas exposure to environmentally relevant aqueous media initiates partial shifts in local Zr coordination and introduces oxygen into the pores – with transformation extent governed by the chemistry of the environmental matrices. Strikingly, acute exposure (24 h) to the water flea Daphnia magna drives profound framework degradation and re-speciation to a homogeneous biotic Zr species. Microfocus XRF maps show that Zr is highly localized in the animal’s digestive tract, and region-specific XANES confirms uniform speciation across its tissues. Our findings establish a cross-compartment transformation hierarchy in which biological processes can dominate the fate of stable MOFs even when abiotic exposures appear benign. Thus, organism-level biotransformation should be performed as a necessary part of environmental safety assessments and materials design.

Some of the largest Mexican uranium (U) deposits are located in Chihuahua. The most important is in Sierra Peña Blanca, northwest of the capital, which was explored and partially exploited in the 1980s. After the closure of activities, the mining projects were left exposed to weathering. To characterize the spread of U minerals towards the neighboring Laguna del Cuervo, sediment samples were collected in the main streams of the drainage pattern of the largest deposits. The U mineral fragments from the fine sand portion were extracted using fluorescence light at 365 nm. The morphology and elemental composition of these particles were analyzed by focused ion beam microscopy (FIB) and scanning transmission electron microscopy (STEM). The particle density in samples close to the U sources was quantified using gamma spectrometry. The highest density was 2500 part./g, and the lowest was 124 part./g. X-ray absorption spectroscopy (XAS) allowed us to establish via XANES the speciation of U in the U particles, confirming the U(VI) oxidation state, while the exploitation of the EXAFS spectrum put in evidence of the presence of uranophane. Finally, the Fe, Sr, and U distributions in the particle and its matrix were obtained via X-ray fluorescence microtomography (XRF-µCT). It was concluded that the particle is composed of uranophane, imbricated with quartz and other oxides.

Some of the largest uranium deposits in Mexico are located in Chihuahua. The most important is in Sierra Peña Blanca, northwest of the capital, which was explored and partially exploited in the 1980s. After the closure of activities, the mining projects were left exposed to weathering. To characterize the drift of uranium minerals towards the neighboring Laguna del Cuervo, sediment samples were collected in the main streams in the drainage pattern of the largest deposits. The uranium mineral fragments from the fine sand portion were extracted using fluorescence at 365 nm light. These particles' morphology and elemental composition were analyzed by focused ion beam microscopy (FIB) and scanning transmission electron microscopy (STEM). The particle density in samples close to the uranium sources was quantified using gamma spectrometry. The highest density was 2500 part./g, and the lowest was 124 part./g. X-ray absorption spectrometry (XAFS) allowed to establish the speciation of U in the urani-um particles, confirming U(VI) through the XANES spectrum. Theoretical fitting of the EXAFS spectrum confirmed the presence of uranophane. Finally, the Fe, Sr, and U dis-tribution in the particle and its matrix was obtained by X-ray fluorescence microto-mography (CT-µXRF). It was concluded that the particle is composed of uranophane, imbricated with quartz and other oxides.

A free-standing and compact reaction cell for combined in situ/operando x-ray spectroscopy, scattering, and imaging measurements at high pressures and high temperatures is described. The cell permits measurements under realistic operating conditions (up to 50 bar and 1000 °C), under static and flow conditions (up to 100 ml/min), over a wide range of hard x-ray energies, variable detection modes (transmission, fluorescence, and scattering), and at all angles of rotation. An operando XAS, x-ray fluorescence, x-ray computed tomography, and x-ray diffraction computed tomography case study on the reduction of a heterogeneous catalyst is presented to illustrate the performance of the reaction cell.

Photo(electro)catalysts use sunlight to drive chemical reactions such as water splitting. A major factor limiting photocatalyst development is physicochemical heterogeneity which leads to spatially dependent reactivity. To link structure and function in such systems, simultaneous probing of the electrochemical environment at microscopic length scales and a broad range of timescales (ns to s) is required. Here, we address this challenge by developing and applying in-situ (optical) microscopies to map and correlate local electrochemical activity, with hole lifetimes, oxygen vacancy concentrations and photoelectrode crystal structure. Using this multi-modal approach, we study prototypical hematite (α-Fe₂O₃) photoelectrodes. We demonstrate that regions of α-Fe₂O₃, adjacent to microstructural cracks have a better photoelectrochemical response and reduced back electron recombination due to an optimal oxygen vacancy concentration, with the film thickness and extended light exposure also influencing local activity. Our work highlights the importance of microscopic mapping to understand activity, in even seemingly homogeneous photoelectrodes.

Uptake of uranium (U) by secondary minerals, such as carbonates and iron (Fe)-sulfides, that occur ubiquitously on Earth, may be substantial in deep anoxic environments compared to surficial settings due to different environment-specific conditions. Yet, knowledge of U reductive removal pathways and related fractionation between ²³⁸U and ²³⁵U isotopes in deep anoxic groundwater systems remain elusive. Here we show bacteria-driven degradation of organic constituents that influences formation of sulfidic species facilitating reduction of geochemically mobile U(VI) with subsequent trapping of U(IV) by calcite and Fe-sulfides. The isotopic signatures recorded for U and Ca in fracture water and calcite samples provide additional insights on U(VI) reduction behaviour and calcite growth rate. The removal efficiency of U from groundwater reaching 75% in borehole sections in fractured granite, and selective U accumulation in secondary minerals in exceedingly U-deficient groundwater shows the potential of these widespread mineralogical sinks for U in deep anoxic environments.

Mineral dust is the largest source of aerosol iron (Fe) to the offshore global ocean, but acidic processing of coal fly ash (CFA) in the atmosphere could be an important source of soluble aerosol Fe. Here, we determined the Fe speciation and dissolution kinetics of CFA from Aberthaw (United Kingdom), Krakow (Poland), and Shandong (China) in solutions which simulate atmospheric acidic processing. In CFA PM₁₀ fractions, 8 %–21.5 % of the total Fe was found to be hematite and goethite (dithionite-extracted Fe), and 2 %–6.5 % was found to be amorphous Fe (ascorbate-extracted Fe), while magnetite (oxalate-extracted Fe) varied from 3 %–22 %. The remaining 50 %–87 % of Fe was associated with other Fe-bearing phases, possibly aluminosilicates. High concentrations of ammonium sulfate ((NH₄)₂SO₄), often found in wet aerosols, increased Fe solubility of CFA up to 7 times at low pH (2–3). The oxalate effect on the Fe dissolution rates at pH 2 varied considerably, depending on the samples, from no impact for Shandong ash to doubled dissolution for Krakow ash. However, this enhancement was suppressed in the presence of high concentrations of (NH₄)₂SO₄. Dissolution of highly reactive (amorphous) Fe was insufficient to explain the high Fe solubility at low pH in CFA, and the modelled dissolution kinetics suggest that other Fe-bearing phases such as magnetite may also dissolve relatively rapidly under acidic conditions. Overall, Fe in CFA dissolved up to 7 times faster than in a Saharan dust precursor sample at pH 2. Based on these laboratory data, we developed a new scheme for the proton- and oxalate-promoted Fe dissolution of CFA, which was implemented into the global atmospheric chemical transport model IMPACT (Integrated Massively Parallel Atmospheric Chemical Transport). The revised model showed a better agreement with observations of Fe solubility in aerosol particles over the Bay of Bengal, due to the initial rapid release of Fe and the suppression of the oxalate-promoted dissolution at low pH. The improved model enabled us to predict sensitivity to a more dynamic range of pH changes, particularly between anthropogenic combustion and biomass burning aerosols.

The Cretaceous-Paleogene (KPg) boundary is demarked by two critical and intimately linked events: a global-scale impact caused by a massive extraterrestrial body, and a resultant catastrophic planet-wide mass-extinction, with pivotal long-term consequences for life on Earth. The site of impact has been identified as the ~180 km wide Chicxulub crater complex [Yucatan peninsula, Mexico] based on strong geochemical, sedimentological, and temporal evidence. However, the impactor, which was obliterated on contact during the cratering process, has eluded identification. Previous studies struggled to identify the projectile based on scant geochemical and isotopic traces admixed with the ejecta and melt-rock, plus a single heavily altered microscopic fragment possibly from the impactor. While those efforts helped to rule out some potential sources and narrowed down the best potential candidates to a CM, CR, or CO carbonaceous chondrite, the data was insufficient to provide an incontrovertible diagnosis, and the identity of the Chicxulub projectile remained a critical missing detail. Here we describe new, exceptionally-preserved fragments of cosmic origin that were directly associated with Chicxulub impact ejecta from a temporally constrained KPg boundary site in North Dakota (U.S.A.). The fragments occur as inclusions within unaltered glassy ejecta spherules, which likely protected them against chemical and physical degradation, leading to their marked preservation. The spherules themselves were also uniquely preserved in amber, which inhibited their usual breakdown to smectitic clay. Geochemical examination of the inclusions were undertaken using electron microprobe, laser-ablation inductively-coupled-plasma-mass-spectroscopy, and synchrotron X-ray techniques. Results provide multiple lines of evidence that support a cosmic origin and chemistry indicative of a CM subtype carbonaceous chondrite, offering new support of prior hypotheses. The data is also in agreement with projectile residues from the Chicxulub impact fallout. In addition to its utility in reconstructing the dynamics of the Chicxulub event, this data helps provide extra dimension to our understanding of major impact processes and their effects on Earth.

Natural uranium (U) in deep groundwater has been extensively studied in connection to the search for suitable locations for final disposal of spent nuclear fuel (SNF).[1] The U removal process depends on environmental and geochemical conditions and is often associated with fractionation of the main ‘stable’ isotopes, 238U and 235U (δ238U). The latter thus serves as an important tracer for redox specific scenarios, in local to global temporal and spatial scales. In this contribution, one specific borehole drilled at 415 m depth into Paleoproterozoic granitoid rock at the Äspö Hard Rock Laboratory (HRL), Sweden, is investigated after 17-year experiment period (1995-2012).[2] The HRL is built and operated by the Swedish Nuclear Fuel and Waste Management Co. and serves as a full-scale tunnel as a test-facility for the actual SNF repository to be built at Forsmark. We show how various micro-analytical techniques, modelling methods, and isotope analyses can be utilized to reveal U speciation and removal pathways, associated redox changes and related U isotope fractionations in the deep aquifer and during U mineralogical trapping. Spectroscopic techniques reveal that calcite precipitated on the borehole equipment contains intermittent highly elevated U, occurring as U(IV), and thus serves as a sink for U. Thermodynamic modelling shows that aqueous Fe(II) is the main driving force for the reduction of U(VI) in the borehole water, alongside sulfides formed from bacterial sulfate reduction. The bacteria-driven degradation of technical polymer constituents present in the borehole equipment is central to processes forming the sulfides and carbonates that facilitate reduction of U(VI) and subsequent immobilisation of U(IV) into the calcite. We use δ238U to show that U undergoes several redox events in granitic rock aquifers, involving mineralogical and microbial pathways. The recorded δ238U provides evidence for reductive removal of U from fracture water, presumably taking place along redox fronts in the fracture network. The obtained data on U(IV) removal by calcite provide important insights for the assessment of the geochemical behaviour of U and other redox-sensitive species in deep anoxic aquifers, that is relevant for trace metal mobility and long-term storage of SNF and nuclear waste.References[1]. J. Suksi et al., (2021), Chemical Geology 584: 120551.[2]. H. Drake et al., (2018), Environmental Science & Technology 52(2): 493-502.