Microbiological and geochemical characterization of As-bearing tailings and underlying sediments.

Over the past 100 years, extensive oxidation of As-bearing sulfide-rich tailings from the abandoned Long Lake Gold Mine (Canada) has resulted in the formation of acid mine drainage (pH 2.0-3.9) containing high concentrations of dissolved As (∼400 mg L-1), SO42-, Fe and other metals. Dissolved As is predominantly present as As(III), with increased As(V) near the tailings surface. Pore-gas O2 is depleted to < 1 vol% in the upper 30-80 cm of the tailings profile. The primary sulfides, pyrite and arsenopyrite, are highly oxidized in the upper portions of the tailings. Elevated proportions of sulfide-oxidizing prokaryotes are present in this zone (mean 32.3% of total reads). The tailings are underlain by sediments rich in organic C. Enrichment in δ34S-SO4 in pore-water samples in the organic C-rich zone is consistent with dissimilatory sulfate reduction. Synchrotron-based spectroscopy indicates an abundance of ferric arsenate phases near the impoundment surface and the presence of secondary arsenic sulfides in the organic-C beneath the tailings. The persistence of elevated As concentrations beneath the tailings indicates precipitation of secondary As sulfides is not sufficient to completely remove dissolved As. The oxidation of sulfides and release of As is expected to continue for decades. The findings will inform future remediation efforts and provide a foundation for the long-term monitoring of the effectiveness of the remediation program.

Improved precision in As speciation analysis with HERFD-XANES at the As K-edge: the case of As speciation in mine waste. Corrigendum.

The name of an author in the article by Saurette et al. (2022) [J. Synchrotron Rad. 29, 1198-1208] is corrected.

Copper-Single-Atom Coordinated Nanotherapeutics for Enhanced Sonothermal-Parallel Catalytic Synergistic Cancer Therapy.

Phototherapy and sonotherapy are recognized by scientific medicine as effective strategies for treating certain cancers. However, these strategies have limitations such as an inability to penetrate deeper tissues and overcome the antioxidant tumor microenvironment. In this study, a novel "BH" interfacial-confined coordination strategy to synthesize hyaluronic acid-functionalized single copper atoms dispersed over boron imidazolate framework-derived nanocubes (HA-NC_Cu) to achieve sonothermal-catalytic synergistic therapy is reported. Notably, HA-NC_Cu demonstrates exceptional sonothermal conversion performance under low-intensity ultrasound irradiation, attained through intermolecular lattice vibrations. In addition, it shows promise as an efficient biocatalyst, able to generate high-toxicity hydroxyl radicals in response to tumor-endogenous hydrogen peroxide and glutathione. Density functional theory calculations reveal that the superior parallel catalytic performance of HA-NC_Cu originates from the CuN4 C/B active sites. Both in vitro and in vivo evaluations consistently demonstrate that the sonothermal-catalytic synergistic strategy significantly improves tumor inhibition rate (86.9%) and long-term survival rate (100%). In combination with low-intensity ultrasound irradiation, HA-NC_Cu triggers a dual death pathway of apoptosis and ferroptosis in MDA-MB-231 breast cancer cells, comprehensively limiting primary triple-negative breast cancer. This study highlights the applications of single-atom-coordinated nanotherapeutics in sonothermal-catalytic synergistic therapy, which may create new opportunities in biomedical research.

Plasmonic nanorod probes' journey inside plant cells for in vivo SERS sensing and multimodal imaging.

Nanoparticle-based platforms are gaining strong interest in plant biology and bioenergy research to monitor and control biological processes in whole plants. However, in vivo monitoring of biomolecules using nanoparticles inside plant cells remains challenging due to the impenetrability of the plant cell wall to nanoparticles beyond the exclusion limits (5-20 nm). To overcome this physical barrier, we have designed unique bimetallic silver-coated gold nanorods (AuNR@Ag) capable of entering plant cells, while conserving key plasmonic properties in the near-infrared (NIR). To demonstrate cellular internalization and tracking of the nanorods inside plant tissue, we used a comprehensive multimodal imaging approach that included transmission electron microscopy (TEM), confocal fluorescence microscopy, two-photon luminescence (TPL), X-ray fluorescence microscopy (XRF), and photoacoustics imaging (PAI). We successfully acquired SERS signals of nanorods in vivo inside plant cells of tobacco leaves. On the same leaf samples, we applied orthogonal imaging methods, TPL and PAI techniques for in vivo imaging of the nanorods. This study first demonstrates the intracellular internalization of AuNR@Ag inside whole plant systems for in vivo SERS analysis in tobacco cells. This work demonstrates the potential of this nanoplatform as a new nanotool for intracellular in vivo biosensing for plant biology.

Non-iridium-based electrocatalyst for durable acidic oxygen evolution reaction in proton exchange membrane water electrolysis.

Iridium-based electrocatalysts remain the only practical anode catalysts for proton exchange membrane (PEM) water electrolysis, due to their excellent stability under acidic oxygen evolution reaction (OER), but are greatly limited by their high cost and low reserves. Here, we report a nickel-stabilized, ruthenium dioxide (Ni-RuO2) catalyst, a promising alternative to iridium, with high activity and durability in acidic OER for PEM water electrolysis. While pristine RuO2 showed poor acidic OER stability and degraded within a short period of continuous operation, the incorporation of Ni greatly stabilized the RuO2 lattice and extended its durability by more than one order of magnitude. When applied to the anode of a PEM water electrolyser, our Ni-RuO2 catalyst demonstrated >1,000 h stability under a water-splitting current of 200 mA cm-2, suggesting potential for practical applications. Density functional theory studies, coupled with operando differential electrochemical mass spectroscopy analysis, confirmed the adsorbate-evolving mechanism on Ni-RuO2, as well as the critical role of Ni dopants in stabilization of surface Ru and subsurface oxygen for improved OER durability.

Solar reduction of carbon dioxide on copper-tin electrocatalysts with energy conversion efficiency near 20.

Copper catalysts modified with tin have been demonstrated to be selective for the electroreduction of carbon dioxide to carbon monoxide. However, such catalysts require the precise control of tin loading amount. Here, we develop a copper/tin-oxide catalyst with dominant tin oxide surface being formed via a spontaneous exchange reaction between sputtered tin and copper oxide. Even though the surface of this catalyst is tin-rich, it achieves an excellent performance towards carbon monoxide production in a flow cell. This contrasts with copper/tin-oxide prepared via atomic layer deposition since it yields selectivity towards carbon monoxide only on a copper-rich surface. Mechanism studies reveal that the tin sites on the tin-rich copper/tin-oxide surface achieve a suitable binding with adsorbed carbon monoxide under the presence of copper. Powered by a triple-junction solar cell, the copper/tin-oxide based electrolyzer sets a new benchmark solar-to-chemical energy conversion efficiency of 19.9 percent with a Faradaic efficiency of 98.9 percent towards carbon monoxide under simulated standard air mass 1.5 global illumination.

Effects of oxygen on the adsorption/oxidation of aqueous Sb(III) by Fe-loaded biochar: An X-ray absorption spectroscopy study.

Fe-loaded biochar (FeBC) has been considered for Sb(III) adsorption, but the effects of oxygen (O2) on the adsorption need further investigation. Liquid-/solid-phase analyses were conducted to investigate the role of O2 in the Sb(III) adsorption by FeBC. The adsorption was best described by the pseudo-second-order (PSO) model for kinetic results and by the Langmuir model for thermodynamic results. More than 96.8 % of Sb(III) was adsorbed by FeBC, and available O2 increased the liquid-phase Sb(III) oxidation efficiency by 2.1-7.5 times. The peak changes at ~1640 and 3450 cm-1 in FTIR spectra indicated the occurrence of inner-sphere complexation between Sb(III)/Sb(V) and hydroxyl (-OH)/carboxyl (-COOH) groups in FeBC under aerobic and anaerobic conditions. Fe/Sb X-ray absorption spectroscopy (XAS) analysis results showed aqueous Sb(III) complexed to the edge-sharing Fe(III)-O-Fe(III) in FeBC. Regardless of whether O2 was available or not, solid-phase edge-sharing Fe(III)-O-Sb(V) complexes (~3.05 Å), which had lower toxicity and migration ability than aqueous Sb(III), formed through a ligand-to-metal charge-transfer (LMCT) process. More than 91 % of adsorbed Sb(III) was oxidized to edge-sharing Fe(III)-O-Sb(V) complexes in 3 h. Additionally, the Sb(V) from liquid-phase oxidation could also directly complex to the Fe(III)-O-Fe(III) and form edge-sharing Fe(III)-O-Sb(V) complexes. These results provide evidence to inform further FeBC application for the Sb-contaminated water treatment.

Iron-modified biochar-based bilayer permeable reactive barrier for Cr(VI) removal.

Iron (Fe)-modified biochar (FeBC) has been developed to remove hexavalent chromium (Cr(VI)) from groundwater and is suitable for use in permeable reactive barriers (PRBs). However, Cr(VI) removal behavior and chemical processes in FeBC-based PRBs are not fully understood, and the potential for Fe release has not been addressed. In this study, three FeBC-based PRBs were assessed in column experiments for 563 days with respect to their ability to remove Cr(VI). Bilayer column filled with FeBC+limestone and BC+limestone in two separate layers (FeBC_Ca_BC) showed the best performance in terms of Cr(VI) removal with a low treatment cost. The corrosion of FeBC was mainly related to pH and Cr(VI) concentration rather than flow rate. Leached Fe was attenuated by BC and limestone and reutilized in FeBC_Ca_BC. Cr(VI) was reduced to Cr(III) and then adsorbed or precipitated on the biochars. Cr and Fe formed inner-sphere complexes and then transformed from double corner sharing to edge sharing. During the reaction, Cr penetrated from the surface to the interior of the biochars and became a more stable species. This study provides evidence of the effectiveness of a new combination of biochars for Cr(VI) removal and insights into the reaction mechanisms.

Efficient conversion of low-concentration nitrate sources into ammonia on a Ru-dispersed Cu nanowire electrocatalyst.

Electrochemically converting nitrate ions, a widely distributed nitrogen source in industrial wastewater and polluted groundwater, into ammonia represents a sustainable route for both wastewater treatment and ammonia generation. However, it is currently hindered by low catalytic activities, especially under low nitrate concentrations. Here we report a high-performance Ru-dispersed Cu nanowire catalyst that delivers an industrial-relevant nitrate reduction current of 1 A cm-2 while maintaining a high NH3 Faradaic efficiency of 93%. More importantly, this high nitrate-reduction catalytic activity enables over a 99% nitrate conversion into ammonia, from an industrial wastewater level of 2,000 ppm to a drinkable water level <50 ppm, while still maintaining an over 90% Faradaic efficiency. Coupling the nitrate reduction effluent stream with an air stripping process, we successfully obtained high purity solid NH4Cl and liquid NH3 solution products, which suggests a practical approach to convert wastewater nitrate into valuable ammonia products. Density functional theory calculations reveal that the highly dispersed Ru atoms provide active nitrate reduction sites and the surrounding Cu sites can suppress the main side reaction, the hydrogen evolution reaction.

With a Little Help from My Cell Wall: Structural Modifications in Pectin May Play a Role to Overcome Both Dehydration Stress and Fungal Pathogens.

Cell wall structural modifications through pectin cross-linkages between calcium ions and/or boric acid may be key to mitigating dehydration stress and fungal pathogens. Water loss was profiled in a pure pectin system and in vivo. While calcium and boron reduced water loss in pure pectin standards, the impact on Allium species was insignificant (p > 0.05). Nevertheless, synchrotron X-ray microscopy showed the localization of exogenously applied calcium to the apoplast in the epidermal cells of Allium fistulosum. Exogenous calcium application increased viscosity and resistance to shear force in Allium fistulosum, suggesting the formation of calcium cross-linkages ("egg-box" structures). Moreover, Allium fistulosum (freezing tolerant) was also more tolerant to dehydration stress compared to Allium cepa (freezing sensitive). Furthermore, the addition of boric acid (H3BO3) to pure pectin reduced water loss and increased viscosity, which indicates the formation of RG-II dimers. The Arabidopsis boron transport mutant, bor1, expressed greater water loss and, based on the lesion area of leaf tissue, a greater susceptibility to Colletotrichum higginsianum and Botrytis cinerea. While pectin modifications in the cell wall are likely not the sole solution to dehydration and biotic stress resistance, they appear to play an important role against multiple stresses.

A general strategy for preparing pyrrolic-N4 type single-atom catalysts via pre-located isolated atoms.

Single-atom catalysts (SACs) have been applied in many fields due to their superior catalytic performance. Because of the unique properties of the single-atom-site, using the single atoms as catalysts to synthesize SACs is promising. In this work, we have successfully achieved Co1 SAC using Pt1 atoms as catalysts. More importantly, this synthesis strategy can be extended to achieve Fe and Ni SACs as well. X-ray absorption spectroscopy (XAS) results demonstrate that the achieved Fe, Co, and Ni SACs are in a M1-pyrrolic N4 (M= Fe, Co, and Ni) structure. Density functional theory (DFT) studies show that the Co(Cp)2 dissociation is enhanced by Pt1 atoms, thus leading to the formation of Co1 atoms instead of nanoparticles. These SACs are also evaluated under hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), and the nature of active sites under HER are unveiled by the operando XAS studies. These new findings extend the application fields of SACs to catalytic fabrication methodology, which is promising for the rational design of advanced SACs.

Binding of histidine and human serum albumin to dirhodium(II) tetraacetate.

Reactions of the anticancer active dirhodium tetraacetate (1), Rh2(AcO)4 (AcO- = CH3COO-), with the amino acid histidine (HHis) and human serum albumin (HSA) were monitored over time and different metal: ligand ratios using UV-vis spectroscopy and/or electro-spray ionization mass spectrometry. Initially, histidine formed 1:1 and 1:2 adducts in aqueous solutions. The crystal structure of Rh2(AcO)4(L-HHis)2·2H2O (2) confirmed the axial coordination of histidine imidazole groups (average Rh-Naxial 2.23 Å). These adducts, however, were found to be unstable in solution over time (24 h). Heating Rh2(AcO)4 -histidine solutions to 40 °C (near body temperature) or 95 °C accelerated the formation of RhII2(AcO)2(His)2 and RhIII(His)2(AcO) complexes. The corresponding pH change from neutral to mildly acid (pH 4-5) indicates deprotonation of histidine NH3+ groups due to coordination to Rh ions, which simultaneously bind to histidine COO- groups, as evidenced by 13C NMR spectroscopy. In the case of HSA with 16 histidine and one cysteine residues, UV-vis spectroscopy indicates that mono- and di-histidine HSA adducts with Rh2(AcO)4 are formed. X-ray absorption spectroscopy showed almost the same Rh-Rh distance (2.41 ± 0.01 Å) for the Rh2(AcO)4 units as in 2, and a contribution from an axial thiol coordination (Rh-Saxial 2.62 ± 0.05 Å). The Rh2(AcO)4 - HSA complex was found to decompose partially (~15%) over 24 h at ambient temperature. The partial decomposition of Rh2(AcO)4 both through coordination to histidine or to human serum albumin, the most abundant protein in blood plasma, is a factor to consider for its efficacy as a potential anticancer agent.

The dual role of oxygen in redox-mediated removal of aqueous arsenic(III/V) by Fe-modified biochar.

The Fe-modified biochar (FeBC) was used to remove aqueous As(III/V), and the role of oxygen (O2) in As removal was investigated by integrating aqueous and solid analyses. The removal efficiencies for As(III) and As(V) increased from 86.4% and 99.2% under anoxic conditions, respectively, to >99.9% when O2 was available. FeBC removed As(III) from As(III)-spiked systems by surface-oxidation following adsorption, where oxidation of As(III) was promoted by O2. As(V) was first reduced, re-oxidized in solutions, and then adsorbed to FeBC in As(V)-spiked systems, where reduction of As(V) was inhibited at the presence of O2. Both As(III) and As(V) were bidentate corner-sharing complexed to Fe oxides/hydroxides on FeBC, with As coordinated to Fe at ~3.4 Å according to As extended X-ray absorption fine structure (EXAFS) modeling. These findings identified the effect of ambient O2 in As(III/V) redox transformations and removal, guiding the further application of FeBC in environmental treatment.

Strain and ligand effects in Pt-Ni alloys studied by valence-to-core X-ray emission spectroscopy.

Experimental detection of the Pt 5d densities of states in the valence band is conducted on a series of Pt-Ni alloys by high energy resolution valence-to-core X-ray emission spectroscopy (VTC-XES) at the Pt L3-edge. VTC-XES measurements reveal that the Pt d-band centroid shifts away from the Fermi level upon dilution, accompanied by concentration-dependent Pt d-band width. The competition between the strain effect and ligand effect is observed experimentally for the first time. It is found that the d-band widths in Pt3Ni and PtNi are broader than that of Pt metal due to compressive strain which overcompensates the effect of dilution, while it is narrower in PtNi3 where the ligand effect dominates. VTC-XES is demonstrated to be a powerful tool to study the Pt d-band contribution to the valence band of Pt-based bimetallic. The implication for the enhanced activity of Pt-Ni catalysts in oxygen reduction reaction is discussed.

Gold-in-copper at low *CO coverage enables efficient electromethanation of CO2.

The renewable-electricity-powered CO2 electroreduction reaction provides a promising means to store intermittent renewable energy in the form of valuable chemicals and dispatchable fuels. Renewable methane produced using CO2 electroreduction attracts interest due to the established global distribution network; however, present-day efficiencies and activities remain below those required for practical application. Here we exploit the fact that the suppression of *CO dimerization and hydrogen evolution promotes methane selectivity: we reason that the introduction of Au in Cu favors *CO protonation vs. C-C coupling under low *CO coverage and weakens the *H adsorption energy of the surface, leading to a reduction in hydrogen evolution. We construct experimentally a suite of Au-Cu catalysts and control *CO availability by regulating CO2 concentration and reaction rate. This strategy leads to a 1.6× improvement in the methane:H2 selectivity ratio compared to the best prior reports operating above 100 mA cm-2. We as a result achieve a CO2-to-methane Faradaic efficiency (FE) of (56 ± 2)% at a production rate of (112 ± 4) mA cm-2.

A cross scale investigation of galena oxidation and controls on mobilization of lead in mine waste rock.

Galena and Pb-bearing secondary phases are the main sources of Pb in the terrestrial environment. Oxidative dissolution of galena releases aqueous Pb and SO4 to the surficial environment and commonly causes the formation of anglesite (in acidic environments) or cerussite (in alkaline environments). However, conditions prevalent in weathering environments are diverse and different reaction mechanisms reflect this variability at various scales. Here we applied complementary techniques across a range of scales, from nanometers to 10 s of meters, to study the oxidation of galena and accumulation of secondary phases that influence the release and mobilization of Pb within a sulfide-bearing waste-rock pile. Within the neutral-pH pore-water environment, the oxidation of galena releases Pb ions resulting in the formation of secondary Pb-bearing carbonate precipitates. Cerussite is the dominant phase and shannonite is a possible minor phase. Dissolved Cu from the pore water reacts at the surface of galena, forming covellite at the interface. Nanometer scale characterization suggests that secondary covellite is intergrown with secondary Pb-bearing carbonates at the interface. A small amount of the S derived from galena is sequestered with the secondary covellite, but the majority of the S is oxidized to sulfate and released to the pore water.

Wireless Optogenetic Modulation of Cortical Neurons Enabled by Radioluminescent Nanoparticles.

While offering high-precision control of neural circuits, optogenetics is hampered by the necessity to implant fiber-optic waveguides in order to deliver photons to genetically engineered light-gated neurons in the brain. Unlike laser light, X-rays freely pass biological barriers. Here we show that radioluminescent Gd2(WO4)3:Eu nanoparticles, which absorb external X-rays energy and then downconvert it into optical photons with wavelengths of ∼610 nm, can be used for the transcranial stimulation of cortical neurons expressing red-shifted, ∼590-630 nm, channelrhodopsin ReaChR, thereby promoting optogenetic neural control to the practical implementation of minimally invasive wireless deep brain stimulation.

Unveiling the Nature of Pt Single-Atom Catalyst during Electrocatalytic Hydrogen Evolution and Oxygen Reduction Reactions.

Single-atom catalysts (SACs) have attracted significant attention due to their superior catalytic activity and selectivity. However, the nature of active sites of SACs under realistic reaction conditions is ambiguous. In this work, high loading Pt single atoms on graphitic carbon nitride (g-C3 N4 )-derived N-doped carbon nanosheets (Pt1 /NCNS) is achieved through atomic layer deposition. Operando X-ray absorption spectroscopy (XAS) is performed on Pt single atoms and nanoparticles (NPs) in both the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR). The operando results indicate that the total unoccupied density of states of Pt 5d orbitals of Pt1 atoms is higher than that of Pt NPs under HER condition, and that a stable Pt oxide is formed during ORR on Pt1 /NCNS, which may suppress the adsorption and activation of O2 . This work unveils the nature of Pt single atoms under realistic HER and ORR conditions, providing a deeper understanding for designing advanced SACs.

Aqua regia digestion cannot completely extract Hg from biochar: A synchrotron-based study.

Mercury (Hg) is commonly extracted from solid phase samples using aqua regia for total Hg (tHg) analysis. However, uncertainties exist regarding the complete extraction of Hg by aqua regia, especially from carbonaceous materials. To investigate whether aqua regia can completely extract Hg from biochars, batch-style experiments were carried out to evaluate extraction efficiency of aqua regia with respect to Hg-loaded biochar and to characterize the residual Hg speciation and spatial distribution. Different types of biochars (raw, FeCl3-modified, and FeSO4-modified, prepared at different temperatures) were reacted with Hg-spiked solution before the digestion experiments. Adsorption analyses indicate the biochars were successfully loaded with Hg and that the Hg content was higher in biochars pyrolyzed at higher temperature (900 versus 300 or 600 °C). The results of digestion experiments indicate Hg could not be completely extracted from the biochars tested, with a greater percentage of residual Hg in biochars pyrolyzed at 600 (60 ± 15%) and 900 (75 ± 22%) than 300 °C (7 ± 2%). Furthermore, the fraction of residual Hg in FeSO4-modified biochars after aqua regia digestion was significantly lower than in FeCl3-modified and unmodified biochars. Confocal micro-X-ray fluorescence imaging (CMXRFI) showed residual Hg in biochars is concentrated on surfaces prior to digestion, but more homogeneously distributed after digestion, which indicates Hg on biochar surface is more easily digested. Hg extended X-ray absorption fine structure (EXAFS) spectra modelling showed residual Hg in biochars mainly exists as Hg(II)-Cl. These results indicate extra caution should be paid for tHg determinations using aqua regia digestion method in soil (especially in forest), sediment, and peat samples containing black carbon, activated carbon, or biochar.

Mechanistic investigation of mercury removal by unmodified and Fe-modified biochars based on synchrotron-based methods.

Improved surface characteristics and incorporated Fe, S, and Cl species are reported in Fe-modified biochar, which makes it a prospective material for Hg(II) removal. In this study, aqueous Hg(II) was removed from solution by unmodified, FeCl3-modified, and FeSO4-modified biochars pyrolyzed at 300, 600, or 900 °C. Higher pyrolytic temperature resulted in higher removal efficiency, with the biochars pyrolyzed at 900 °C removing >96% of Hg(II). Fe-modification enhanced Hg(II) removal for biochars pyrolyzed at 600 °C (from 88% to >95%) or 900 °C (from 96% to 99%). Based on synchronous extended X-ray absorption fine structure (EXAFS) analysis, Hg coordinated to S in modified and unmodified biochars pyrolyzed at 900 °C, where thiol was reported, and in FeSO4-modified biochars pyrolyzed at 600 or 900 °C, where sulfide was recognized; in other biochars, Hg bound to O or Cl. Additionally, confocal micro-X-ray fluorescence imaging (CMXRFI) demonstrated Hg was distributed in agreement with S in biochars where HgS was formed; otherwise, Hg distribution was influenced by Hg species in solution and the pore characteristics of the biochar. This investigation provides information on the effectiveness and mechanisms of Hg removal that is critical for evaluating biochar applications and optimizing modification methods in groundwater remediation.