Slab melting boosts the mantle wedge contribution to Li-rich magmas.

The lithium cycling in the supra-subduction mantle wedge is crucial for understanding the generation of Li-rich magmas that may potentially source ore deposition in continental arcs. Here, we look from the mantle source perspective at the geological processes controlling the Li mobility in convergent margins, by characterizing a set of sub-arc mantle xenoliths from the southern Andes (Coyhaique, western Patagonia). The mineral trace element signatures and oxygen fugacity estimates (FMQ > + 3) in some of these peridotite xenoliths record the interaction with arc magmas enriched in fluid-mobile elements originally scavenged by slab dehydration. This subduction-related metasomatism was poorly effective on enhancing the Li inventory of the sub-arc lithospheric mantle, underpinning the inefficiency of slab-derived fluids on mobilizing Li through the mantle wedge. However, major and trace element compositions of mantle minerals in other xenoliths also record transient thermal and chemical anomalies associated with the percolation of slab window-related magmas, which exhibit an "adakite"-type geochemical fingerprint inherited by slab-derived melts produced during ridge subduction and slab window opening event. As these melts percolated through the shallow (7.2-16.8 kbar) and hot (952-1054 °C) lithospheric mantle wedge, they promoted the crystallization of metasomatic clinopyroxene having exceptionally high Li abundances (6-15 ppm). Numerical modeling shows that low degrees (< 10%) of partial melting of this Li-rich and fertile sub-arc lithospheric mantle generates primitive melts having two-fold Li enrichment (~13 ppm) compared with average subduction-zone basalts. Prolonged fractional crystallization of these melts produces extremely Li-enriched silicic rocks, which may stoke the Li inventory of mineralizing fluids in the shallow crust.

High-entropy engineering of the crystal and electronic structures in a Dirac material.

Dirac and Weyl semimetals are a central topic of contemporary condensed matter physics, and the discovery of new compounds with Dirac/Weyl electronic states is crucial to the advancement of topological materials and quantum technologies. Here we show a widely applicable strategy that uses high configuration entropy to engineer relativistic electronic states. We take the AMnSb2 (A = Ba, Sr, Ca, Eu, and Yb) Dirac material family as an example and demonstrate that mixing of Ba, Sr, Ca, Eu and Yb at the A site generates the compound (Ba0.38Sr0.14Ca0.16Eu0.16Yb0.16)MnSb2 (denoted as A5MnSb2), giving access to a polar structure with a space group that is not present in any of the parent compounds. A5MnSb2 is an entropy-stabilized phase that preserves its linear band dispersion despite considerable lattice disorder. Although both A5MnSb2 and AMnSb2 have quasi-two-dimensional crystal structures, the two-dimensional Dirac states in the pristine AMnSb2 evolve into a highly anisotropic quasi-three-dimensional Dirac state triggered by local structure distortions in the high-entropy phase, which is revealed by Shubnikov-de Haas oscillations measurements.

Nanomaterial accumulation in boiling brines enhances epithermal bonanzas.

Epithermal bonanza-type ores, characterized by weight-percent contents of e.g., gold and silver in a few mm to cm, are generated by mixtures of magmatic-derived hydrothermal brines and external fluids (e.g., meteoric) that transport a variety of metals to the site of deposition. However, the low solubilities of precious metals in hydrothermal fluids cannot justify the high concentrations necessary to produce such type of hyper-enriched metal ore. Here we show that boiling metal-bearing brines can produce, aggregate, and accumulate metal nanomaterials, ultimately leading to focused gold + silver ± copper over-enrichments. We found direct nano-scale evidence of nanoparticulate gold- and/or silver-bearing ores formed via nonclassical growth (i.e., nanomaterial attachment) during boiling in an intermediate-sulfidation epithermal bonanza. The documented processes may explain the generation of bonanzas in metal-rich brines from a range of mineral deposit types.

A track record of Au-Ag nanomelt generation during fluid-mineral interactions.

Recent studies have reported the significant role of Au-bearing nanoparticles in the formation of hydrothermal gold deposits. Despite the ever-increasing understanding of the genesis and stability of Au-bearing nanoparticles, it is still unknown how they behave when exposed to hydrothermal fluids. Here, we study the nanostructural evolution of Au-Ag nanoparticles hosted within Co-rich diarsenides and sulfarsenides of a natural hydrothermal deposit. We use high-resolution transmission electron microscopy to provide a singular glimpse of the complete melting sequence of Au-Ag nanoparticles exposed to the hydrothermal fluid during coupled dissolution-precipitation reactions of their host minerals. The interaction of Au-Ag nanoparticles with hydrothermal fluids at temperatures (400-500 ºC) common to most hydrothermal gold deposits may promote melting and generation of Au-Ag nanomelts. This process has important implications in noble metal remobilization and accumulation during the formation of these deposits.

Mechanisms for Pd-Au enrichment in porphyry-epithermal ores of the Elatsite deposit, Bulgaria.

Porphyry Cu can contain significant concentrations of platinum-group elements (PGE: Os, Ir, Ru, Rh, Pt, Pd). In this study, we provide a comprehensive in situ analysis of noble metals (PGE, Au, Ag) for (Cu-Fe)-rich sulfides from the Elatsite, one of the world's PGE-richest porphyry Cu deposits. These data, acquired using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), indicate that Pd was concentrated in all the (Cu-Fe)-rich sulfides at ppm-levels, with higher values in pyrite (~6 ppm) formed at the latest epithermal stage (i.e., quartz-galena-sphalerite assemblage) than in bornite and chalcopyrite (<5 ppm) from the hypogene quartz-magnetite-bornite-chalcopyrite ores. Likewise, Au is significantly more concentrated in pyrite (~5 ppm) than in the (Cu-Fe)-rich sulfides (≤0.08 ppm). In contrast, Ag reaches hundreds of ppm in pyrite and bornite (~240 ppm) but is in much lesser amounts in chalcopyrite (<25 ppm). The inspection of the time-resolved spectra collected during LA-IPC-MS analyses indicates that noble metals are present in the sulfides in two forms: (1) structurally bound (i.e., solid solution) in the lattice of sulfides and, (2) as nano- to micron-sized inclusions (Pd-Te and Au). These observations are further confirmed by careful investigations of the PGE-rich (Cu-Fe)-rich sulfides by combining high-spatial resolution of field emission scanning electron microscope (FESEM) and focused ion beam and high-resolution transmission electron microscopy (FIB/HRTEM). A typical Pd-bearing mineral includes the composition PdTe2 close to the ideal merenskyite but with a distinct crystallographic structure, whereas Au is mainly found as native element. Our detailed mineralogical study coupled with previous knowledge on noble-metal inclusions in the studied ores reveals that noble metal enrichment in the Elatsite porphyry ores was mainly precipitated from droplets of Au-Pd-Ag telluride melt (s) entrained in the high-temperature hydrothermal fluid. These telluride melts could separate at the time of fluid unmixing from the silicate magma or already be present in the latter either derived from deep-seated crustal or mantle sources. Significant enrichment in Pd and Au (the latter correlated with As) in low-temperature pyrite is interpreted as remobilization of these noble metals from pre-existing hypogene ores during the epithermal overprinting.

Fluxing of mantle carbon as a physical agent for metallogenic fertilization of the crust.

Magmatic systems play a crucial role in enriching the crust with volatiles and elements that reside primarily within the Earth's mantle, including economically important metals like nickel, copper and platinum-group elements. However, transport of these metals within silicate magmas primarily occurs within dense sulfide liquids, which tend to coalesce, settle and not be efficiently transported in ascending magmas. Here we show textural observations, backed up with carbon and oxygen isotope data, which indicate an intimate association between mantle-derived carbonates and sulfides in some mafic-ultramafic magmatic systems emplaced at the base of the continental crust. We propose that carbon, as a buoyant supercritical CO2 fluid, might be a covert agent aiding and promoting the physical transport of sulfides across the mantle-crust transition. This may be a common but cryptic mechanism that facilitates cycling of volatiles and metals from the mantle to the lower-to-mid continental crust, which leaves little footprint behind by the time magmas reach the Earth's surface.

Plume-subduction interaction forms large auriferous provinces.

Gold enrichment at the crustal or mantle source has been proposed as a key ingredient in the production of giant gold deposits and districts. However, the lithospheric-scale processes controlling gold endowment in a given metallogenic province remain unclear. Here we provide the first direct evidence of native gold in the mantle beneath the Deseado Massif in Patagonia that links an enriched mantle source to the occurrence of a large auriferous province in the overlying crust. A precursor stage of mantle refertilisation by plume-derived melts generated a gold-rich mantle source during the Early Jurassic. The interplay of this enriched mantle domain and subduction-related fluids released during the Middle-Late Jurassic resulted in optimal conditions to produce the ore-forming magmas that generated the gold deposits. Our study highlights that refertilisation of the subcontinental lithospheric mantle is a key factor in forming large metallogenic provinces in the Earth's crust, thus providing an alternative view to current crust-related enrichment models.The lithospheric controls on giant gold deposits remain unclear. Here, the authors show evidence for native gold in the mantle from the Deseado Massif in Patagonia demonstrating that refertilisation of the lithospheric mantle is key in forming metallogenic provinces.

Assessing the risk of phosphorus transfer to high ecological status rivers: Integration of nutrient management with soil geochemical and hydrological conditions.

Agriculture has been implicated in the loss of pristine conditions and ecology at river sites classified as at 'high ecological status' across Europe. Although the exact causes remain unclear, diffuse phosphorus (P) transfer warrants consideration because of its wider importance for the ecological quality of rivers. This study assessed the risk of P loss at field scale from farms under contrasting soil conditions within three case-study catchments upstream of near-pristine river sites. Data from 39 farms showed P surpluses were common on extensive farm enterprises despite a lower P requirement and level of intensity. At field scale, data from 520 fields showed that Histic topsoils with elevated organic matter contents had low P reserves due to poor sorption capacities, and received applications of P in excess of recommended rates. On this soil type 67% of fields recorded a field P surplus of between 1 and 31kgha-1, accounting for 46% of fields surveyed across 10 farms in a pressured high status catchment. A P risk assessment combined nutrient management, soil biogeochemical and hydrological data at field scale, across 3 catchments and the relative risks of P transfer were highest when fertilizer quantities that exceeded current recommendations on soils with a high risk of mobilization and high risk of transport as indicated by topographic wetness index values. This situation occurred on 21% of fields surveyed in the least intensively managed catchment with no on-farm nutrient management planning and soil testing. In contrast, the two intensively managed catchments presented a risk of P transfer in only 3% and 1% of fields surveyed across 29 farms. Future agri-environmental measures should be administered at field scale, not farm scale, and based on soil analysis that is inclusive of OM values on a field-by-field basis.

Resonance energy transfer between tryptophan-214 in human serum albumin and acrylodan, prodan, and promen.

It has been proposed that acrylodan (6-acryloyl-2-dimethylaminonaphthalene) and prodan (6-propionyl-2-dimethylaminonaphthalene) bind to site I of human serum albumin, whereas promen (6-propionyl-2-methoxynaphthalene) binds to site II of this carrier protein. Because human albumin contains only one single tryptophan, at position 214, it has been possible to measure the distances from this amino-acid residue to each of the three probes by nonradiative energy transfer. The distances calculated, 2.97 +/- 0.10 nm, 3.14 +/- 0.11 nm, and 2.62 +/- 0.17 nm, respectively, confirm the locations previously proposed for all three probes.

Urea-induced denaturation of human serum albumin labeled with acrylodan.

We induced the denaturation of unlabeled human serum albumin (HSA) and of similar albumin labeled with acrylodan (6-acryloyl-2-dimethylamino naphthalene) with urea and studied the transition profiles using circular dichroism and fluorescence spectroscopy. The circular dichroism spectra for both albumin preparations resulted in the same curves, thus indicating that labeling with acrylodan does not perturb the conformation of HSA. Our results indicate that the denaturation of both albumin preparations takes place at a single, two-state transition with midpoint at about 6 M urea, due to the unfolding of its domain II. It is important to point out that even at 8 M urea, some residual structure remains in the HSA. Great changes in the fluorescence of the dye bound to the protein were observed by addition of solid guanidine hydrochloride to the protein labeled with acrylodan dissolved in 8 M urea, indicating that domain I of this protein was not denatured by urea.