Multiple Rounds of In Vivo Random Mutagenesis and Selection in Vibrio natriegens Result in Substantial Increases in REE Binding Capacity.

Rare earth elements (REE) are essential ingredients in many modern technologies, yet their purification remains either environmentally harmful or economically unviable. Adsorption, or biosorption, of REE onto bacterial cell membranes offers a sustainable alternative to traditional solvent extraction methods. But in order for biosorption-based REE purification to compete economically, the capacity and specificity of biosorption sites must be enhanced. Although there have been some recent advances in characterizing the genetics of REE-biosorption, the variety and complexity of bacterial membrane surface sites make targeted genetic engineering difficult. Here, we propose using multiple rounds of in vivo random mutagenesis induced by the MP6 plasmid combined with plate-throughput REE-biosorption screening to improve a microbe's capacity and selectivity for biosorbing REE. We engineered a strain of Vibrio natriegens capable of biosorbing 210% more dysprosium compared to the wild-type and produced selectivity improvements of up to 50% between the lightest (lanthanum) and heaviest (lutetium) REE. We believe that mutations we observed in ABC transporters as well as a nonessential protein in the BAM outer membrane ß-barrel protein insertion complex likely contribute to some─but almost certainly not all─of the biosorption changes we observed. Given the ease of finding significant biosorption mutants, these results highlight just how many genes likely contribute to biosorption as well as the power of random mutagenesis in identifying genes of interest and optimizing a biological system for a task.

Phases in fine volcanic ash.

Volcanic ash emissions impact atmospheric processes, depositional ecosystems, human health, and global climate. These effects are sensitive to the size and composition of the ash; however, datasets describing the constituent phases over size ranges relevant for atmospheric transport and widely distributed impacts are practically nonexistent. Here, we present results of X-ray diffraction measurements on size-separated fractions of 40 ash samples from VEI 2-6 eruptions. We characterize changes in phase fractions with grainsize, tectonic setting, and whole-rock SiO2. For grainsizes < 45 µm, average fractions of crystalline silica and surface salts increased while glass and iron oxides decreased with respect to the bulk sample. Samples from arc and intraplate settings are distinguished by feldspar and clinopyroxene fractions (determined by different crystallization sequences) which, together with glass, comprise 80-100% of most samples. We provide a dataset to approximate glass-free proportions of major crystalline phases; however, glass fractions are highly variable. To tackle this, we describe regressions between glass and major crystal phase fractions that help constrain the major phase proportions in volcanic ash with limited a priori information. Using our dataset, we find that pore-free ash density is well-estimated as a function of the clinopyroxene + Fe-oxide fraction, with median values of 2.67 ± 0.01 and 2.85 ± 0.03 g/cm3 for intraplate and arc samples, respectively. Finally, we discuss effects including atmospheric transport and alteration on modal composition and contextualize our proximal airfall ash samples with volcanic ash cloud properties. Our study helps constrain the atmospheric and environmental budget of the phases in fine volcanic ash and their effect on ash density, integral to refine our understanding of the impact of explosive volcanism on the Earth system from single eruptions to global modeling.

Genomic characterization of rare earth binding by Shewanella oneidensis.

Rare earth elements (REE) are essential ingredients of sustainable energy technologies, but separation of individual REE is one of the hardest problems in chemistry today. Biosorption, where molecules adsorb to the surface of biological materials, offers a sustainable alternative to environmentally harmful solvent extractions currently used for separation of rare earth elements (REE). The REE-biosorption capability of some microorganisms allows for REE separations that, under specialized conditions, are already competitive with solvent extractions, suggesting that genetic engineering could allow it to leapfrog existing technologies. To identify targets for genomic improvement we screened 3,373 mutants from the whole genome knockout collection of the known REE-biosorbing microorganism Shewanella oneidensis MR-1. We found 130 genes that increased biosorption of the middle REE europium, and 112 that reduced it. We verified biosorption changes from the screen for a mixed solution of three REE (La, Eu, Yb) using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) in solution conditions with a range of ionic strengths and REE concentrations. We identified 18 gene ontologies and 13 gene operons that make up key systems that affect biosorption. We found, among other things, that disruptions of a key regulatory component of the arc system (hptA), which regulates cellular response to anoxic environments and polysaccharide biosynthesis related genes (wbpQ, wbnJ, SO_3183) consistently increase biosorption across all our solution conditions. Our largest total biosorption change comes from our SO_4685, a capsular polysaccharide (CPS) synthesis gene, disruption of which results in an up to 79% increase in biosorption; and nusA, a transcriptional termination/anti-termination protein, disruption of which results in an up to 35% decrease in biosorption. Knockouts of glnA, pyrD, and SO_3183 produce small but significant increases (≈ 1%) in relative biosorption affinity for ytterbium over lanthanum in multiple solution conditions tested, while many other genes we explored have more complex binding affinity changes. Modeling suggests that while these changes to lanthanide biosorption selectivity are small, they could already reduce the length of repeated enrichment process by up to 27%. This broad exploratory study begins to elucidate how genetics affect REE-biosorption by S. oneidensis, suggests new areas of investigation for better mechanistic understanding of the membrane chemistry involved in REE binding, and offer potential targets for improving biosorption and separation of REE by genetic engineering.

Oceanic intraplate explosive eruptions fed directly from the mantle.

Constraining the volatile content of magmas is critical to our understanding of eruptive processes and their deep Earth cycling essential to planetary habitability [R. Dasgupta, M. M. Hirschmann, Earth Planet. Sci. Lett. 298, 1 (2010)]. Yet, much of the work thus far on magmatic volatiles has been dedicated to understanding their cycling through subduction zones. Further, studies of intraplate mafic volcanism have disproportionately focused on Hawaii [P. E. Wieser et al., Geochem. Geophys. Geosyst. 22, e2020GC009364 (2021)], making assessments of the overall role of intraplate volcanoes in the global volatile cycles a challenge. Additionally, while mafic volcanoes are the most common landform on Earth and the Solar System [C. A. Wood, J. Volcanol. Geotherm. Res. 7, 387-413 (1980)], they tend to be overlooked in favor of silicic volcanoes when it comes to their potential for explosivity. Here, we report primitive (olivine-hosted, with host Magnesium number - Mg# 78 to 88%) melt inclusion (MI) data from Fogo volcano, Cabo Verde, that suggest that oceanic intraplate silica-undersaturated explosive eruptions sample volatile-rich sources. Primitive MI (melt Mg# 70 to 71%) data suggest that these melts are oxidized (NiNiO to NiNiO+1) and very high in volatiles (up to 2 wt% CO2, 2.8 wt% H2O, 6,000 ppm S, 1,900 ppm F, and 1,100 ppm Cl) making Fogo a global endmember. Storage depths calculated from these high volatile contents also imply that magma storage at Fogo occurs at mantle depths (~20 to 30 km) and that these eruptions are fed from the mantle. Our results suggest that oceanic intraplate mafic eruptions are sustained from the mantle by high volatile concentrations inherited from their source and that deep CO2 exsolution (here up to ~800 MPa) drives their ascent and explosivity.

The evolution of the Galápagos mantle plume.

The lavas associated with mantle plumes may sample domains throughout Earth's mantle and probe its dynamics. However, plume studies are often only able to take snapshots in time, usually of the most recent plume activity, leaving the chemical and geodynamic evolution of major convective upwellings in Earth's mantle poorly constrained. Here, we report the geodynamically key information of how the lithology and density of a plume change from plume head phase to tail. We use iron stable isotopes and thermodynamic modeling to show that the Galápagos plume has contained small, nearly constant, amounts of dense recycled crust over its 90-million-year history. Despite a temporal evolution in the amount of recycled crust-derived melt in Galápagos-related lavas, we show that this can be explained by plume cooling alone, without associated changes in the plume's mantle source; results are also consistent with a plume rooted in a lower mantle low-velocity zone also sampling primordial components.

Deep magma storage during the 2021 La Palma eruption.

The 2021 La Palma eruption provided an unpreceded opportunity to test the relationship between earthquake hypocenters and the location of magma reservoirs. We performed density measurements on CO2-rich fluid inclusions (FIs) hosted in olivine crystals that are highly sensitive to pressure via calibrated Raman spectroscopy. This technique can revolutionize our knowledge of magma storage and transport during an ongoing eruption, given that it can produce precise magma storage depth constraints in near real time with minimal sample preparation. Our FIs have CO2 recorded densities from 0.73 to 0.98 g/cm3, translating into depths of 15 to 27 km, which falls within the reported deep seismic zone recording the main melt storage reservoir.

Serpentinite-derived slab fluids control the oxidation state of the subarc mantle.

Recent geochemical evidence confirms the oxidized nature of arc magmas, but the underlying processes that regulate the redox state of the subarc mantle remain yet to be determined. We established a link between deep subduction-related fluids derived from dehydration of serpentinite ± altered oceanic crust (AOC) using B isotopes and B/Nb as fluid proxies, and the oxidized nature of arc magmas as indicated by Cu enrichment during magma evolution and V/Yb. Our results suggest that arc magmas derived from source regions influenced by a greater serpentinite (±AOC) fluid component record higher oxygen fugacity. The incorporation of this component into the subarc mantle is controlled by the subduction system's thermodynamic conditions and geometry. Our results suggest that the redox state of the subarc mantle is not homogeneous globally: Primitive arc magmas associated with flat, warm subduction are less oxidized overall than those generated in steep, cold subduction zones.

High 3He/4He in central Panama reveals a distal connection to the Galápagos plume.

It is well established that mantle plumes are the main conduits for upwelling geochemically enriched material from Earth's deep interior. The fashion and extent to which lateral flow processes at shallow depths may disperse enriched mantle material far (>1,000 km) from vertical plume conduits, however, remain poorly constrained. Here, we report He and C isotope data from 65 hydrothermal fluids from the southern Central America Margin (CAM) which reveal strikingly high 3He/4He (up to 8.9RA) in low-temperature (≤50 °C) geothermal springs of central Panama that are not associated with active volcanism. Following radiogenic correction, these data imply a mantle source 3He/4He >10.3RA (and potentially up to 26RA, similar to Galápagos hotspot lavas) markedly greater than the upper mantle range (8 ± 1RA). Lava geochemistry (Pb isotopes, Nb/U, and Ce/Pb) and geophysical constraints show that high 3He/4He values in central Panama are likely derived from the infiltration of a Galápagos plume-like mantle through a slab window that opened ∼8 Mya. Two potential transport mechanisms can explain the connection between the Galápagos plume and the slab window: 1) sublithospheric transport of Galápagos plume material channeled by lithosphere thinning along the Panama Fracture Zone or 2) active upwelling of Galápagos plume material blown by a "mantle wind" toward the CAM. We present a model of global mantle flow that supports the second mechanism, whereby most of the eastward transport of Galápagos plume material occurs in the shallow asthenosphere. These findings underscore the potential for lateral mantle flow to transport mantle geochemical heterogeneities thousands of kilometers away from plume conduits.

Generation of a Gluconobacter oxydans knockout collection for improved extraction of rare earth elements.

Bioleaching of rare earth elements (REEs), using microorganisms such as Gluconobacter oxydans, offers a sustainable alternative to environmentally harmful thermochemical extraction, but is currently not very efficient. Here, we generate a whole-genome knockout collection of single-gene transposon disruption mutants for G. oxydans B58, to identify genes affecting the efficacy of REE bioleaching. We find 304 genes whose disruption alters the production of acidic biolixiviant. Disruption of genes underlying synthesis of the cofactor pyrroloquinoline quinone (PQQ) and the PQQ-dependent membrane-bound glucose dehydrogenase nearly eliminates bioleaching. Disruption of phosphate-specific transport system genes enhances bioleaching by up to 18%. Our results provide a comprehensive roadmap for engineering the genome of G. oxydans to further increase its bioleaching efficiency.

Author Correction: Sampling the volatile-rich transition zone beneath Bermuda.

An Amendment to this paper has been published and can be accessed via a link at the top of the paper.

Sampling the volatile-rich transition zone beneath Bermuda.

Intraplate magmatic provinces found away from plate boundaries provide direct sampling of the composition and heterogeneity of the Earth's mantle. The chemical heterogeneities that have been observed in the mantle are usually attributed to recycling during subduction1-3, which allows for the addition of volatiles and incompatible elements into the mantle. Although many intraplate volcanoes sample deep-mantle reservoirs-possibly at the core-mantle boundary4-not all intraplate volcanoes are deep-rooted5, and reservoirs in other, shallower boundary layers are likely to participate in magma generation. Here we present evidence that suggests Bermuda sampled a previously unknown mantle domain, characterized by silica-undersaturated melts that are substantially enriched in incompatible elements and volatiles, and a unique, extreme isotopic signature. To our knowledge, Bermuda records the most radiogenic 206Pb/204Pb isotopes that have been documented in an ocean basin (with 206Pb/204Pb ratios of 19.9-21.7) using high-precision methods. Together with low 207Pb/204Pb ratios (15.5-15.6) and relatively invariant Sr, Nd, and Hf isotopes, the data suggest that this source must be less than 650 million years old. We therefore interpret the Bermuda source as a previously unknown, transient mantle reservoir that resulted from the recycling and storage of incompatible elements and volatiles6-8 in the transition zone (between the upper and lower mantle), aided by the fractionation of lead in a mineral that is stable only in this boundary layer, such as K-hollandite9,10. We suggest that recent recycling into the transition zone, related to subduction events during the formation of Pangea, is the reason why this reservoir has only been found in the Atlantic Ocean. Our geodynamic models suggest that this boundary layer was sampled by disturbances related to mantle flow. Seismic studies and diamond inclusions6,7 have shown that recycled materials can be stored in the transition zone11. For the first time, to our knowledge, we show geochemical evidence that this storage is key to the generation of extreme isotopic domains that were previously thought to be related only to deep recycling.

Record of massive upwellings from the Pacific large low shear velocity province.

Large igneous provinces, as the surface expression of deep mantle processes, play a key role in the evolution of the planet. Here we analyse the geochemical record and timing of the Pacific Ocean Large Igneous Provinces and preserved accreted terranes to reconstruct the history of pulses of mantle plume upwellings and their relation with a deep-rooted source like the Pacific large low-shear velocity Province during the Mid-Jurassic to Upper Cretaceous. Petrological modelling and geochemical data suggest the need of interaction between these deep-rooted upwellings and mid-ocean ridges in pulses separated by ∼10-20 Ma, to generate the massive volumes of melt preserved today as oceanic plateaus. These pulses impacted the marine biota resulting in episodes of anoxia and mass extinctions shortly after their eruption.

Petrological evidence for secular cooling in mantle plumes.

Geological mapping and geochronological studies have shown much lower eruption rates for ocean island basalts (OIBs) in comparison with those of lavas from large igneous provinces (LIPs) such as oceanic plateaux and continental flood provinces. However, a quantitative petrological comparison has never been made between mantle source temperature and the extent of melting for OIB and LIP sources. Here we show that the MgO and FeO contents of Galapagos-related lavas and their primary magmas have decreased since the Cretaceous period. From petrological modelling, we infer that these changes reflect a cooling of the Galapagos mantle plume from a potential temperature of 1,560-1,620 degrees C in the Cretaceous to 1,500 degrees C at present. Iceland also exhibits secular cooling, in agreement with previous studies. Our work provides quantitative petrological evidence that, in general, mantle plumes for LIPs with Palaeocene-Permian ages were hotter and melted more extensively than plumes of more modern ocean islands. We interpret this to reflect episodic flow from lower-mantle domains that are lithologically and geochemically heterogeneous.

Presencia de radionucleidos en arcillas del sistema hidrotermal del Volcán Turrialba, Costa Rica

Los primeros resultados de un estudio sobre la presencia de algunos radionucleidos de origen terrígeno, son presentados para el sistema hidrotermal del volcán Turrialba. Se tomaron muestras de arcillas en varios puntos de los cráteres central y suroeste y se analizaron mediante espectrometría gamma de bajo nivel, usando un detector de germanio hiperpuro. Se reportan los valores de las actividades en Bq/kg, de los isótopos radiactivos naturales detectados. Se encontró un desequilibrio en la serie del U-238, el cual es explicado por dos mecanismos diferentes: uno de índole convectivo y el otro por enriquecimiento de Rn-222. Se observa un aumento en la actividad de todos los isótopos entre setiembre del 2001 y mayo del 2002. Dada la poca probabilidad de que este aumento se deba a la escorrentía superficial, se propone que el aumento de la concentración de estos elementos puede ser ocasionado por su llegada en la fase gaseosa, suspendidos en el vapor de agua y otros gases volcánicos.(AU)