Metal Carrier Research Articles

UV-Aged Nanoplastics Increase Mercury Toxicity in a Marine Copepod under Multigenerational Exposure: A Carrier Role.

Aged plastics possess diverse interactive properties with metals compared to pristine ones. However, the role of aging for nanoplastics (NPs) in being a carrier of mercury (Hg), a common marine environmental pollutant, and their combined effects remain unclear. This study investigated the carrier effect of ultraviolet-aged NPs on Hg and the ensuing toxicity in a marine copepod Tigriopus japonicus under a multigenerational scenario. Aged NPs revealed a better carrier role in Hg bioaccumulation than pristine ones, which was increased by 1.61, 1.52, and 1.54 times in F0, F1, and F2, respectively, probably attributed to increased levels of O-containing functional groups and better adsorption for Hg. Consequently, relative to Hg alone, Hg combined with aged NPs (rather than pristine ones) significantly compromised the copepod's fitness, e.g., the survival rate decreasing by 74.2 and 62.1% in F1 and F2, respectively. This is possibly linked to the most pronounced transcriptomic response under Hg combined with aged NPs, including disturbed cuticle formation, activated antioxidants, and down-regulation of reproductive genes. Overall, our findings emphasize the non-negligible risk of aged NPs as carriers of toxic metals and provide a better understanding about the long-term effects of coexisting NPs and metal pollution on organisms in real marine environments.

Magmatic initial and saturated water thresholds determine copper endowments: Insights from apatite F-Cl-OH compositions

Magmatic volatiles (H2O, F, Cl), especially water, are critical in the formation of porphyry copper deposit, for its significance as a carrier for metals. However, accurately quantifying the water contents of deep ore-forming magma remain a challenge. Here, we used apatite and forward modelling methods to reconstruct magmatic water evolution histories, with special concern on the control of initial magmatic H2O contents and water saturation threshold to porphyry mineralization. Samples investigated include granitoid rocks and apatite from highly copper-mineralized and barren localities. Generally, our research suggested that both ore-related and ore-barren magma systems are hydrous, the modeled magmatic water contents vary significantly among systems whether mineralized or not, and the major difference lies in the threshold of water saturation (6.0 wt.% for barren, and up to 10.0 wt.% for highly mineralized). Combined with whole rock geochemistry data (high K2O and Sr/Y contents) and modeling result (high modeled water thresholds), we think the ore-related magmas are stored at deeper depth with higher water solubility. In conclusion, we propose that the level of magmatic water saturation plays a crucial role in the formation of porphyry copper systems. Fertile magma has higher water solubility to which deeper storage depth is a critical contributing factor, and can get significantly water enriched upon saturation.

Decadal trends of black carbon and heavy metal accumulation in a lake sediment core from central China: A historical perspective

Black carbon (BC) and heavy metal are vital indicators of historical human activities. This study investigates the historical pollution trends of BC, char, soot, and heavy metals in lake sediments from Yinjia Lake (YJL). BC, char, and soot concentrations exhibit similar historical trends, with average values of 1.59, 1.27, and 0.32 mg/g, respectively. Char, constituting 67.25–85.85 % of BC, indicates a dominant fraction in the lake. A notable increase in BC, char, and soot was observed post-1955, peaking in 2005, followed by a decline, reflecting local economic development and anthropogenic activities. Heavy metals, including Cu, Cd, Zn, Pb, Cr, Co, Ni, and Mn, also displayed a significant increase post-1950, with Cd showing an exceptionally high concentration. The average deposition fluxes of BC, char, and soot were consistent with their concentrations, peaking in 2005. The correlations between BC, char, soot, and heavy metals suggest BC’s role as a metal carrier, influenced by industrial and anthropogenic emissions. The char/soot ratio analysis indicates predominant biomass burning pre-1950 and increased fossil fuel combustion post-1950, with regional variations observed. The study highlights the impact of industrialization, urbanization, and policy changes on pollution trends in YJL.

Petroleum evolution and its genetic relationship with the associated Jinding Pb[sbnd]Zn deposit in Lanping Basin, Southwest China

The spatial association of hydrocarbons with metalliferous ore deposits is found worldwide and is particularly common to MVT PbZn deposits. Heavy oil and bitumen are found in the Jinding PbZn deposit within the Lanping Basin, South China. However, the temporal and genetic associations between hydrocarbons and the deposit are still controversial. To this end, integrating Raman analysis, ReOs geochronology and transmission electron microscopy analysis of the bitumen and in situ S isotope analyses of the sulfide, the petroleum evolution of the Jinding reservoir and its genetic relationship with the PbZn deposits were discussed. Bitumen ReOs data from this study and published works indicate that the late Triassic shales underwent two distinct oil-generation events before mineralisation (∼25 Ma), with initial oil generation occurring during the early Cretaceous (∼116 Ma) and the second during the early Paleogene (ca. 68–59 Ma). These two ages agree with the modelled thermal history of the Jinding reservoir. Combining the oil-before-ore timing sequence, high metal abundance of the bitumen, two negative sulfur isotope peaks of the sulfide and high S/C atomic ratio of the bitumen from the Jinding deposit, the oil-containing aqueous solutions were considered as one metal carrier during the hydrocarbon migration and accumulation; further, bacterial sulfate reduction and thermo-chemically induced sulfate reduction processes could have participated in the supply of reduced sulfur for the PbZn deposit precipitation.

Uncovering the Intrinsic High Fracture Toughness of Titanium via Lowered Oxygen Impurity Content.

Titanium (Ti) and its alloys are known to exhibit room-temperature fracture toughness below 130 MPa m1/2, only about one half of the best austenitic stainless steels. It is purported that this is not the best possible fracture resistance of Ti, but a result of oxygen impurities that sensitively retard the activities of plasticity carriers in this hexagonal close-packed metal. By a reduction of oxygen content from the 0.14wt% in commercial purity Ti to 0.02wt%, the mode-Ι fracture toughness of the low-oxygen Ti is measured to be as high as KJ Ic ≈ 255 MPa m1/2, corresponding to J-integral-based crack-initiation toughness of up to JIc ≈ 537kJ m-2. This extraordinary toughness, reported here for the first time for pure Ti, places Ti among the toughest known materials. The intrinsic high fracture resistance is attributed to the profuse plastic deformation in a significantly enlarged plastic zone, rendered by the pronounced deformation twinning ahead of the crack tip along with ample twin-stimulated 〈c+a〉 dislocation activities, in the absence of impeding oxygen. Controlling the content of a property-controlling impurity thus holds the promise to be a readily applicable strategy to reach for unprecedented damage tolerance in some other structural alloys.

Size-Dependent Elemental Composition in Individual Magnetite Nanoparticles Generated from Coal-Fired Power Plant Regulating Their Pulmonary Cytotoxicity.

High-resolution characterization of magnetite nanoparticles (MNPs) derived from coal combustion activities is crucial to better understand their health-related risks. In this study, size distribution and elemental composition of individual MNPs from various coal fly ashes (CFAs) collected from a representative coal-fired power plant were analyzed using a single-particle inductively coupled plasma time-of-flight mass spectrometry technique. Majority (61-80%) of MNPs were identified as multimetal (mm)-MNPs, while the contribution of single metal (sm)-MNPs to the total increased throughout all the CFAs, reaching the highest in fly ash escaped through the stack (EFA). Among Fe-rich MNPs, Fe-sole and Fe-Al matrices were predominant, and Fe-sole MNPs were identified as the important carrier for toxic metals, with the highest mass contributions of toxic metals therein. Toxic potency results showed that the oxidative stress induced by MNPs was 1.2-2.2 times greater than those of <1 μm fractions in CFAs, while the reduction in cell viability showed no significant difference, elucidating that these MNPs can induce more distinct oxidative stress compared to cell toxicity. Based on structural equation model, MNP size can both directly and indirectly regulate the toxic potency, and the indirect regulation is through a size-dependent elemental composition of MNPs, including toxic metals. sm-MNPs and Fe-rich MNPs with Fe-sole, Fe-Cr, and Fe-Zn matrices can regulate the oxidative stress, whereas Cr, Zn, and Pb associated with Fe-sole, Fe-Al, Si-Fe, and Al-Fe MNPs showed significant effects on cell viability.

Current density–voltage characteristics of exciplex-type organic light-emitting diodes expressed by a simple analytic equation

Exciplex-type bilayer organic light-emitting diodes (OLEDs) with ohmic contacts exhibited current density–voltage (J–V) characteristics that closely matched a simplified analytical model proposed by Nikitenko and Bässler. The analytical model is based on the following key assumptions: (i) complete hole–electron recombination at the interface between a hole transport layer (HTL) and an electron transport layer (ETL), (ii) ohmic contacts at the interfaces between metal electrodes and carrier transport layers, and (iii) electric-field-independent carrier mobilities in both HTL and ETL. The excellent matching shows that the simplified analytical model is sufficient to describe the J–V characteristics of the OLEDs. We also demonstrated that if the carrier mobility of one carrier transport layer is known, that of the other transport layer can be estimated using the equation derived by the simplified analytical model. The simplified analytical model provides a useful method to estimate carrier mobilities within carrier transport layers themselves in OLEDs.

Universal correlation between H-linear magnetoresistance and T-linear resistivity in high-temperature superconductors

The signature feature of the ‘strange metal’ state of high-Tc cuprates—its linear-in-temperature resistivity—has a coefficient α1 that correlates with Tc, as expected were α1 derived from scattering off the same bosonic fluctuations that mediate pairing. Recently, an anomalous linear-in-field magnetoresistance (=γ1H) has also been observed, but only over a narrow doping range, leaving its relation to the strange metal state and to the superconductivity unclear. Here, we report in-plane magnetoresistance measurements on three hole-doped cuprate families spanning a wide range of temperatures, magnetic field strengths and doping. In contrast to expectations from Boltzmann transport theory, γ1 is found to correlate universally with α1. A phenomenological model incorporating real-space inhomogeneity is proposed to explain this correlation. Within this picture, superconductivity in hole-doped cuprates is governed not by the strength of quasiparticle interactions with a bosonic bath, but by the concentration of strange metallic carriers.

The combined toxicity of polystyrene microplastic and arsenate: From the view of biochemical process in wheat seedlings (Triticum aestivum L.)

Microplastics (MPs) are important carriers of various toxic metals and can alter their toxicity pattern in agricultural soil, leading to combined pollution, therefore posing new challenges to soil pollution management and environmental risk assessment. In this study, we observed the internalization of MPs in plants and conducted incubation experiments to evaluated the effects of arsenate (As(V)) alone and in combination with polystyrene (PS) MPs on wheat seedlings (Triticum aestivum L.). Under As(V) alone and combined with PS-MP exposure, dose-dependent toxicity in terms of root and stem elongation and biomass accumulation was observed. Compared with As(V) alone, the presence of PS-MPs reduced the accumulation of As in wheat roots by 11.43–58.91%, but PS-MPs intensified the transport of As to the aboveground parts of wheat, increasing As accumulation in wheat stems by 27.77–1011.54%. This causes more serious mechanical damage and oxidative stress to plant cells, increasing the accumulation of reactive oxygen species and lipid peroxidation in wheat roots and upregulating the activities of antioxidant enzymes such as superoxide dismutase (SOD) and peroxidase (POD). In addition, the co-exposure of As(V) and PS-MPs disrupts the photosynthetic system of wheat leaves and the secretion activities of roots. Therefore, the combination of As(V) and PS-MPs caused greater damage to wheat growth. Our findings contribute to a more comprehensive assessment of the combined toxicity of MPs and heavy metal to crops.

Preparation Method of a Metal Carrier for a Catalyst for the Recovery of Exhaust Gases from Nitrogen Oxides

The article shows the process of preparing an oxide layer on the surface of titanium for use in industrial catalysis. Data from physical and chemical studies are presented, namely microhardness, porosity, thickness, specific surface area, adhesion and thermal stability of the active layer.To determine the physicochemical characteristics of the resulting oxide layer, the following analysis methods were used: X-ray diffraction analysis (XRD), X-ray diffraction phase analysis (XPA), X-ray absorption analysis (XRA), and X-ray fluorescence analysis. The thickness of the oxide layer depending on the duration of anodization was estimated by optical microscopy.

Interactions between microplastics and heavy metals in leachate: Implications for landfill stabilization process

The emission of microplastics and heavy metals in landfills has attracted widespread attention for its stabilization process. Microplastics have become carriers of heavy metals due to their adsorption properties, affecting their environmental behavior. However, the effects of landfill stabilization on the interaction between microplastics and heavy metals in leachate are ambiguous. This work explored the abundance characteristics of microplastics and heavy metals in leachate from 10 landfills in Beijing. Overall, the average abundance of microplastics was 196.3 items/L, dominated by small particle size (20–50 µm) and film microplastics. The levels of Cr and As were much higher than other heavy metals. The average abundance of microplastics and polymer types tended to decrease as the landfill stabilization proceeded, and the surface composition of microplastics became more complex. Statistical analysis revealed that the correlations between microplastics and heavy metals in the leachate of landfill stabilization presented significant parabolic characteristics, and Cr and As were more susceptible to landfill stabilization with significant positive correlation with a wide range of microplastics such as 20–30 µm. These results were intended to provide a scientific basis for the treatment and disposal of waste leachate and the synergistic prevention and control of new and traditional pollutants.

The Application Progress of Nonthermal Plasma Technology in the Modification of Bone Implant Materials.

With the accelerating trend of global aging, bone damage caused by orthopedic diseases, such as osteoporosis and fractures, has become a shared international event. Traffic accidents, high-altitude falls, and other incidents are increasing daily, and the demand for bone implant treatment is also growing. Although extensive research has been conducted in the past decade to develop medical implants for bone regeneration and healing of body tissues, due to their low biocompatibility, weak bone integration ability, and high postoperative infection rates, pure titanium alloys, such as Ti-6A1-4V and Ti-6A1-7Nb, although widely used in clinical practice, have poor induction of phosphate deposition and wear resistance, and Ti-Zr alloy exhibits a lack of mechanical stability and processing complexity. In contrast, the Ti-Ni alloy exhibits toxicity and low thermal conductivity. Nonthermal plasma (NTP) has aroused widespread interest in synthesizing and modifying implanted materials. More and more researchers are using plasma to modify target catalysts such as changing the dispersion of active sites, adjusting electronic properties, enhancing metal carrier interactions, and changing their morphology. NTP provides an alternative option for catalysts in the modification processes of oxidation, reduction, etching, coating, and doping, especially for materials that cannot tolerate thermodynamic or thermosensitive reactions. This review will focus on applying NTP technology in bone implant material modification and analyze the overall performance of three common types of bone implant materials, including metals, ceramics, and polymers. The challenges faced by NTP material modification are also discussed.

Mineralogy of Zinc and Lead Metallurgical Slags in Terms of Their Impact on the Environment: A Review

This paper presents the results of a study of the mineralogical and chemical composition of zinc and lead metallurgical slags. These slags contain numerous elements, including toxic metals, which form conglomerates or multiphase intergrowths. The phase composition of slags is one of the main factors that determine their behaviour in weathering environments, that is, their ability to release metals when exposed to atmospheric factors. In this paper, the release of elements from slags and their mobility in a hypergenic environment is determined based on the results of leachability tests and on geochemical modelling, thus assessing the environmental impact of landfilled slags. The elements released from slags in the largest quantities are zinc and lead. Zn is leached out over a long period of time. It was found that after 12 years, the concentration of Zn in the eluate exceeds by 40 times the permissible value of 200 mg/kg for hazardous waste. The degree of leaching of lead from slags as a function of time (after 12 years), despite its significant solubility in water, is much lower than the degree of leaching of zinc. The most mobile phase components of slags in the studied hypergenic environment are the lead phases (anglesite and galena) and, to a lesser extent, the zinc phases (sphalerite and willemite). Anglesite and galena in almost the entire Eh-pH range, along with admixtures of elements, decompose into ionic forms: PbCl42−, Pb2+, and PbOH+. Sphalerite in the soil and water environment (oxidizing and acidic conditions) will decompose into the mobile ionic form Zn2+. Willemite, which is resistant to weathering, will undergo similar decomposition. It can therefore be assumed that the carriers of toxic metals are primarily lead sulphides and sulphates, zinc sulphides, and, less frequently, zinc, lead, and iron oxides.

(Invited) Unraveling Hot Carrier Transfer Processes in Plasmonic Catalysis

In the last decade, plasmonic nanoantennas have revolutionized light manipulation and control at the nanoscale. Interestingly, generation of hot carriers in metals upon light absorption have opened new pathways for controlling photo(electro)chemical processes and engineering photocatalysts. Yet, fundamental questions remain about the microscopic details of these complex light-matter interactions.We have recently developed a well-controlled platform for micro-scale plasmonic photoelectrochemistry studies that leverages the unique properties of monocrystalline microflakes [1] as well as precise nanofabrication methods. Interestingly, the microflakes exhibit well-defined crystal facets and can bridge the properties of bulk metals with those of nanoscale plasmonic antennas, accessing ultra-thin film dimensions (sub 15-nm) that are challenging for polycrystalline films. By performing careful absorption measurements, we explore the photoelectrochemical performance of these hot carrier micro-scale photoelectrodes for inner- and outer-sphere reactions [2], concurrently comparing them to cm-scale devices [3]. This allows us to unravel the interplay of hot carrier generation and transport at metal-liquid and metal-semiconductor interfaces and identify bottlenecks for charge transfer.[1] Kiani F., Tagliabue G. - High‐Aspect Ratio Au Microflakes via Gap‐Assisted Synthesis – Chemistry of Materials 34 (3), 1278-1288, 2022[2] Kiani F. et al - Transport and Interfacial Injection of d-band Hot Holes Control Plasmonic Chemistry - ACS Energy Letters, 8 (10), 4242-4250, 2023[3] Ma J., Oh K., Tagliabue G. - Understanding Wavelength-Dependent Synergies between Morphology and Photonic Design in TiO2-Based Solar Powered Redox Cells – Journal of Physical Chemistry C, 127 (1), 11-21, 2022

Local Reinforcement of a Fuel Cell End Plate for Package Improvements Using Steel–Aluminium Hybrid-Casting Technology

In this research work, a method for integrating a local reinforcement structure in a medium-pressure plate (MPP) for fuel cell electric vehicle (FCEV) applications was developed using steel–aluminium hybrid-casting technology. Using this technology, it is possible to create a bonded enclosure of a steel reinforcement patch with the cast aluminium pressure plate to increase its stiffness and achieve 15% package space savings. A load-compliant, manufacturable patch was chosen and optimised for maximum stiffness gains using non-linear static finite-element (FE) calculations. Special form and process requirements due to hybrid-casting technology were examined and secured with casting simulations. The reinforcement patch was manufactured and coated with a unique aluminium–silicon coating enabling a ductile material connection between the steel and aluminium, and casting trials were conducted to create prototypes. Additionally, the insulating plastic layer on top of the metallic pressure plate carrier was substituted from costly short-fibre-reinforced high-performance plastic to cheaper and stiffer glass-mat reinforced thermoplastic material. Finally, the new hybrid MPP was tested mechanically, and the FE-Model was verified. In summary, through the package gain, 2.1 kW more power output and 11% less weight could be achieved while remaining stiffness neutral.

Właściwości i zastosowanie gruzińskiego naturalnego filipsytu

Oceanic and terrestrial sedimentary phillipsites make up very large reserves, but the use of this natural zeolite is not so wide comparing to clinoptilolite, and purpose of our study was to characterize the phillipsites of the Georgian deposits and highlight their possible application. It is shown that natural phillipsite can be used as a raw material for the synthesis of phase-pure zeolite NaX with Si/Al~1.5-1.7 in the form of octahedral crystallites with uniform micrometric (2-7 μm) dimensions, characterized by high specific surface area (590-770 m2/g) and volume of pores (0.58 cm3/g) including uniform zeolitic micropores and channels with an average diameter of 55 nm, which opens up the prospect of its use in catalysis. It has been established that natural phillipsite is a suitable carrier of bioactive metals: silver-, copper-, and zinc-containing micro-mesoporous materials have been prepared using ion-exchange reactions between zeolite and a salt of a transition metal; the products contain up to 235 mg/g of silver, 85 mg/g of copper, and 87 mg/g of zinc, and in the Kirby-Bauer disk-diffusion test show strong bacteriostatic activity against such microorganisms as gram-negative bacterium Escherichia coli, gram-positive bacteria Staphylococcus aureus and Bacillus subtilis, fungal pathogenic yeast Candida albicans and a fungus Aspergilus niger. The use of bactericidal materials obtained on the basis of natural phillipsite is possible both for water purification and disinfection, and as fillers in the production of polymeric materials, paper and cardboard.

Fe-Co PBA/rGO interface strategy enabling fast Al3+ intercalation for stable aqueous Al-ion batteries

Aqueous aluminum-ion batteries (AAIBs) have emerged as cost-effective and safe alternatives to lithium-ion batteries for storing energy. However, utilizing cathode materials like Prussian blue analogs (PBAs) to accommodate different metallic charge carriers faces challenges due to their low conductivity and slow redox kinetics. To overcome these issues, we propose a novel Fe-Co PBA/rGO nanocomposite with a strong interfacial chemical coupling between Fe-Co PBA and rGO. By combining theoretical calculations with experimental analysis, we have identified the essential role of interfacial interactions in regulating the electronic state and diffusion barriers of Al3+ within the Fe-Co PBA framework. Moreover, a three-dimensional structure that is tightly enclosed by ultrathin rGO sheets was successfully formed, ensuring excellent structural stability. Ex-situ XPS and XRD investigations have further clarified the electrochemical mechanism of the Fe-Co PBA/rGO cathode, revealing reversible redox reactions between Fe2+/Fe3+ and Co3+/Co2+ states during the insertion and extraction of Al3+. These inherent properties contribute to the remarkable cycling stability of the Fe-Co PBA/rGO cathode, achieving 66.7 mAh/g at 1 A/g after 1500 cycles, and high electrochemical reversibility. Additionally, we have successfully built a MoO3//Fe-Co PBA/rGO full battery with a capacity of 53.6 mAh/g over 2000 cycles at 1 A/g. This outcome further emphasizes its significant potential in electronic applications related to energy storage.

Ultrafast relaxation dynamics of excited carriers in metals: Simplifying the intertwined dependencies upon scattering strengths, phonon temperature, photon energy, and excitation level

Ultrafast relaxation dynamics of excited carriers in metals: Simplifying the intertwined dependencies upon scattering strengths, phonon temperature, photon energy, and excitation level

Regulating the Co 3d center of Co3O4 by Co3O4/g-C3N4 to enhance electronic activity for sulfamethizole effectively degaradtion by permonosulfate activation

The Permonosulfate (PMS) activation via Co based catalysts have been recognized as the most effective PMS activation method. However, regulating the Co-3d band center of Co based catalysts to enhance PMS activation is still a challenge. Since g-C3N4 is often a good carrier for transition metals and their oxides, in this work, the Co3O4/g-C3N4 was developed by a simple way to modulate the Co-3d band center of Co3O4 and was used to sulfamethizole (STZ) degradation. Also, some characterizations demonstrated the Co3O4/g-C3N4 has been successfully prepared such as Transmission electron microscope (TEM), X-ray Diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). It also showed an effective removal efficiency for STZ by PMS activation (k1 = 0.77 min−1). The reactive oxygen species (ROS) quenching experiments verified the main ROS are 1O2 and SO4•−. The DFT results indicated that the Co-3d of Co3O4 band center (from −1.78 eV to −1.41 eV) was successfully modulated, further improving the electronic utilization efficiency and electronic activity, thus effective PMS activation was obtained. This work not only provided a potential way to antibiotics removal in water, but also offered a mechanism analysis of PMS activation by Co-based catalysts in depth.

Nernst Effect of High-Mobility Weyl Electrons in NdAlSi Enhanced by a Fermi Surface Nesting Instability

The thermoelectric Nernst effect of solids converts heat flow to beneficial electronic voltages. Here, using a correlated topological semimetal with high carrier mobility μ in the presence of magnetic fluctuations, we demonstrate an enhancement of the Nernst effect close to a magnetic phase transition. A magnetic instability in NdAlSi modifies the carrier relaxation time on “hot spots” in momentum space, causing a strong band filling dependence of μ. We quantitatively derive electronic band parameters from a novel two-band analysis of the Nernst effect Sxy, in good agreement with quantum oscillation measurements and band calculations. While the Nernst response of NdAlSi behaves much like conventional semimetals at high temperatures, an additional contribution ΔSxy from electronic correlations appears just above the magnetic transition. Our work demonstrates the engineering of the relaxation time, or the momentum-dependent self-energy, to generate a large Nernst response independent of a material’s carrier density, i.e., for metals, semimetals, and semiconductors with large μ. Published by the American Physical Society 2024