Search Results (680)

Permian sedimentary manganese carbonate deposits in the Qiling Basin exhibit substantial resource potential, yet their depositional environments and precipitation pathways remain insufficiently constrained. This study integrates petrographic, mineralogical, whole-rock geochemical, and carbonate C–O isotope data from the Shuibutou Mn deposit in southern Hunan. We compare this deposit with the coeval Dongxiangqiao deposit and other Permian marine sedimentary Mn deposits to constrain its depositional setting, Mn-carbonate precipitation mechanisms, and potential Mn sources. The Shuibutou ores contain 10.88–17.18 wt.% MnO and are characterized by spherulitic–oolitic textures, abundant bioclasts, and framboidal pyrite. Mo–U enrichment indicates anoxic bottom waters, whereas the near-marine δ¹³C_carb values of ore carbonates (−0.24‰ to 1.28‰) are consistent with precipitation within a marine carbonate system and suggest direct precipitation of Mn(II) carbonates from dissolved Mn²⁺ under anoxic conditions. In this setting, dissolved Mn²⁺ accumulated below the chemocline. Partial dissolution of platform-derived calcite grains near the chemocline increased local dissolved inorganic carbon and alkalinity, driving Mn-carbonate supersaturation and the authigenic precipitation of manganoan calcite, ultimately forming manganese carbonate ores. The low Al/(Al + Fe + Mn) ratios, high Fe/Ti ratios, and Co–Ni–Zn and REY geochemical characteristics are consistent with a possible contribution from Mn-rich deep fluids to the dissolved Mn²⁺ inventory of the basin waters. Similarities in mineralogy, geochemistry, and depositional setting between Shuibutou and Dongxiangqiao point to a possible regional role for the direct precipitation of Mn(II) carbonates under anoxic conditions in the Middle Permian Qiling Basin. Relatively deep intraplatform basins may therefore represent favorable targets for manganese carbonate exploration and provide a reference for exploration targeting of Permian sedimentary Mn deposits within the Qiling Basin. Full article

Trace element contamination represents a persistent environmental issue, particularly in industrialized areas where anthropogenic emissions overlap with natural geochemical backgrounds. This study investigates the atmospheric deposition of trace elements in the Milazzo district (Italy), which is characterized by intense industrial activity. Pinus pinea L. needles were used as biomonitors to assess the spatial distribution and sources of trace elements, combined with lead isotopic analysis for source apportionment. Forty needle samples were analyzed by ICP-OES and ICP-MS for Ca, K, Mg, Na, P, Al, As, Ba, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Ti, V, Zn, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, while 25 samples were selected for Pb isotope ratio determination (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb). Multivariate statistical analyses identified source groups related to industrial and petrochemical emissions, vehicular traffic, crustal resuspension, and mixed combustion processes. Elevated concentrations of As, Cr, Mo, Ni, Pb, Sb, V, and Zn ranged from 16.6 μg g⁻¹ (Zn) to 0.09 μg g⁻¹ (Sb), with the following order of abundance: Zn > Cr > Ni > Pb > Mo > V > As > Sb; these elements were found near industrial facilities and urban areas. Enrichment Factor calculations indicated strong anthropogenic contributions to Cd, Cu, Mo, Sb, V, and Zn, with EF > 10, ranging from 10 (Cd) to 60 (Zn), whereas Al, Fe, and Ti exhibited EF values between 0.5 and 2, reflecting geogenic origins. Pb isotopic ratios (²⁰⁶Pb/²⁰⁷Pb = 1.153–1.192 and ²⁰⁸Pb/²⁰⁶Pb = 2.063–2.108) revealed mixing between industrial emissions and the local geological background, with limited influence from historical gasoline-derived Pb. This integrated geochemical and isotopic approach can effectively identify contamination sources in complex industrial environments. Full article

Microbially induced calcium carbonate precipitation (MICP) is a promising biotechnology for environmental remediation; however, the high cost of conventional chemical-grade calcium sources limits its large-scale scalability. This study evaluated the feasibility of utilizing an aqueous extract of natural attapulgite clay as a sustainable, low-cost calcium source for MICP-mediated arsenic (As) immobilization in both aqueous and soil systems. Among the tested minerals, Baiyin attapulgite (group B) exhibited the highest calcium content (62,808.94 mg kg⁻¹) and minimal toxic metal impurities, providing a favorable chemical matrix for biomineralization. At an optimal solid-to-liquid ratio of 1:10, Lysinibacillus fusiformis LF and Enterococcus LZU-1 successfully induced calcite precipitation driven by the attapulgite extract. In batch aqueous remediation experiments (20 days), the attapulgite extract significantly enhanced As removal efficiency compared to the controls; As removal rates peaked at 66.4% for strain LZU-1 (with LZ1 extract) and 65.8% for strain LF (with group B extract), drastically outperforming the standard CaCl₂ groups (31.2–37.3%) and blank controls (21.8–24.5%). Concurrently, soil incubation experiments (30 days) demonstrated that the combined application of attapulgite and MICP bacteria reduced the highly bioavailable exchangeable As fraction from 0.115 to approximately 0.03 mg kg⁻¹, while effectively driving its transformation into more stable carbonate-bound and organic-bound fractions without causing secondary soil salinization. Morphological and mechanistic analyses revealed that, compared to the well-defined euhedral crystals in the CaCl₂ control, the precipitates mediated by the clay extract exhibited distinctly irregular, defect-rich rhombohedral structures. This structural disruption was governed by the natural matrix effect of attapulgite, which simultaneously supplied dissolved Ca²⁺ and provided an abundance of fine clay fragments, calcite micro-grains, and associated amorphous Fe/Al/Mn-bearing phases. These constituents acted as physical scaffolding and heterogeneous nucleation sites that became embedded in the growing CaCO₃ lattice, driving the formation of highly reactive, defect-rich clay-calcite-arsenic composite precipitates that efficiently encapsulated arsenate. Mantel analysis further revealed that the remediation efficiency was significantly correlated with key environmental variables including Ni, V, Ca. These findings highlight the dual-system potential of natural attapulgite as an inexpensive, eco-friendly calcium alternative for sustainable MICP-based remediation of As-contaminated water and agricultural soils. Full article

Selective laser melting (SLM) can effectively suppress metallurgical defects inherent to conventional manufacturing; however, subsequent aging treatments essential for engineering applications introduce secondary precipitates that alter the electrochemical homogeneity of the matrix. The underlying mechanism by which such precipitation behavior governs corrosion resistance remains elusive. In this study, a Fe-30Mn-8Al-1.5C-2.5Ni steel was investigated to elucidate the corrosion morphology and electrochemical behavior of the as-built, 450 °C-aged, and 750 °C-aged specimens during immersion in a 3.5 wt.% NaCl solution. The results demonstrate that the inherent Mn microsegregation and high-density subgrain boundaries induced by SLM trigger preferential localized anodic dissolution on the surface of the as-built sample, culminating in the formation of a loose, porous manganese oxide product layer. Aging treatment at 450 °C induces extensive precipitation of κ-carbides within grain interiors and along grain boundaries, accompanied by localized depletion of Al and Mn at the phase interfaces. A pronounced micro-galvanic coupling established between the κ-carbides and the adjacent Al-depleted zones directly compromises the continuity of the passive film, thereby further deteriorating the corrosion resistance. In contrast, aging at 750 °C relieves the residual stress and eliminates the as-built elemental microsegregation. The resulting compositional homogenization of the matrix reduces the localized electrochemical driving force, which promotes a uniform reaction of Al at the surface to construct a continuous, compact Al-rich passive film, thereby sustaining the highest charge-transfer resistance during long-term immersion. This work elucidates the correlation among the intrinsic defects of SLM, aging-induced solute-depleted zones, κ-carbide precipitation, and localized micro-galvanic corrosion, providing a fundamental basis for tailoring the microstructure and corrosion resistance of additively manufactured lightweight steels. Full article

In this study, we examined the mineralogy, geochemistry and origin of Fe–Mn mineralization occurring as lenses within siliceous mudstones of the Middle Eocene Maden Complex (Durmuştepe, Elazığ, Türkiye) using multivariate statistical methods and Compositional Data Analysis (CoDA). Major-oxide, trace-element and REE analyses were performed on 21 samples (n = 21), comprising 11 ore and 10 host-rock samples. Ore microscopy, discrimination diagrams, PAAS-normalized REE patterns, Principal Component Analysis (PCA), Hierarchical Cluster Analysis (HCA), factor analysis, Kendall correlation and CLR-transformed CoDA-PCA were applied. The ore consists of pyrolusite, braunite, manganite, magnetite and hematite. Massive and felty textures indicate rapid precipitation linked to abrupt physicochemical changes near the vents. Fe/Mn ≈ 1.62 and Co/Ni = 0.03–0.04 support an exhalative origin; Ce/Ce* = 0.10–0.15 (mean 0.11) records a pronounced negative Ce anomaly; and Eu/Eu* = 1.06–1.18 suggests vent-fluid temperatures below ~250 °C. CoDA-PCA shows that Ce is decoupled from the other lanthanides; HCA separates ore from host-rock populations; and factor analysis indicates that Ti–Al–K detrital input diluted ore accumulation. Integrating these results, we interpret Durmuştepe as a proximal volcano-sedimentary hydrothermal-exhalative Fe–Mn system that formed during magmatism in the Maden marginal basin under oxic seawater mixing and contemporaneous detrital sedimentation. The multivariate workflow also provides a reproducible approach for source characterization in similar mixed-origin deposits. Full article

This study evaluated trace element bioaccumulation in Nile tilapia (Oreochromis niloticus) marketed in Brazil and assessed potential implications for food safety and human health. A total of 120 farmed fish samples, including whole fish and tissues (gills, kidneys, liver, and muscle), were analyzed. Concentrations of Al, As, Cr, Cu, Fe, Mn, Ni, Pb, Se, and Zn were determined by inductively coupled plasma optical emission spectrometry (ICP-OES) and compared with ANVISA and FAO/WHO guideline values. Arsenic concentrations complied with ANVISA limits, whereas Pb in whole Nile tilapia exceeded the permissible threshold. Nickel and Se concentrations in muscle and whole fish also surpassed FAO/WHO guidelines. Estimated Se intake from consumption of whole tilapia and muscle (fillet) reached 188.01% of the Recommended Dietary Allowance (RDA) for children aged 8 years. Contamination index values (CI) indicated bioaccumulation of Ni in multiple tissues and Se in edible portions. Human health risk assessment identified carcinogenic risks associated with As, Cr, Ni, and Pb, while non-carcinogenic risk (HI > 1) was primarily driven by As exposure. These findings highlight the need for continuous monitoring of trace elements in aquaculture products. Full article

In this study, CoCrFeNiMn high-entropy alloys (HEAs) with different aluminum (Al) contents were fabricated, and the effects of Al content on the microstructure evolution and mechanical properties were systematically explored. The microstructural characterization results indicated that the Al content exerted a crucial regulatory effect on the crystal structure of the alloy. With increasing Al content, shifts in the characteristic XRD peaks indicate lattice expansion of the alloy. Meanwhile, the phase structure continuously evolved from a single face-centered cubic (FCC) structure to an FCC/body-centered cubic (BCC) dual-phase structure, and then finally transformed into a BCC-dominated structure. Appropriate Al element addition could produce localized stress fields near dislocations and achieve prominent solid-solution strengthening, which effectively inhibited dislocation movement and further improved the yield strength, tensile strength, and hardness of the alloy. In contrast, excessive Al addition would break through the solid solubility limit of the alloy matrix, causing obvious phase separation and the precipitation of brittle B2-ordered NiAl-type intermetallic secondary phases. These brittle secondary phases easily induced crack initiation in the plastic deformation process, which significantly deteriorated the ductility, work-hardening ability, and impact toughness of the alloys. Full article

High-entropy alloys (HEAs) are a transformative class of materials with remarkable structural and functional properties. Solid-state processing techniques, such as high-energy ball milling, are being increasingly used for their production. In these processes, the use of a process control agent (PCA) seems to be essential to prevent excessive cold welding and agglomeration; however, the influence of different PCAs on alloy formation remains insufficiently understood. This study systematically examined the effects of the PCA type, milling configuration, and elemental substitution on HEAs mechanosynthesis. A non-equiatomic alloy, Al₁₀Cr₁₂Fe₃₅Mn₂₃Ni₂₀ (selected for its known single-phase Face Center Cubic (FCC) behavior), was used to explore the PCA and mill-type effects. The alloy was synthesized in a planetary mill (Fritsch Pulverisette 7) and a vibratory mill (SPEX 8000M) using diverse PCAs, including liquid (methanol, ethanol, isopropyl, and n-heptane) and solid (stearic acid and sodium chloride) agents. In addition, lightweight equiatomic alloys MgAlTiNi(Co,Cr,Fe) were used to explore the influence of different PCAs and the effect of elemental substitution under similar PCA conditions as those used with the equiatomic alloy. The products were characterized using X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and differential thermal analysis techniques. The results highlighted that the PCA selection, milling configuration, and alloy chemistry influenced the phase evolution, particle size distribution, and thermal behavior. The results provide insights into the mechanosynthesis of selected high-entropy alloys produced under different PCA and milling conditions. Full article

Sedimentary manganese deposits are an important mineral resource and also play a significant role in restoring the ancient marine environment. The redox environment of the ocean during the Mesoproterozoic era has long been a subject of controversy. This paper takes a large-scale sedimentary manganese deposit in northwest China as the research object, attempting to analyze the changes in the marine environment during the Mesoproterozoic era and their impact on the Mn mineralization processes. In recent years, an exploration breakthrough has been made in the manganese deposits in the Annanba region on the southern margin of the Dunhuang block, NW China. The Qingshagou Mn deposit is the largest and most representative in the region. Geochemical characteristics show that the ores have low average ratios of Fe/Mn (<0.19), V/Cr (<1.20), V/(V + Ni) (<0.54), and Al/(Al + Fe + Mn) (<0.30) but high average ratios of U/Th (~0.95), and Y/Ho (~28). The Post-Archean Australian Shale (PAAS)-normalized rare earth element (REE) patterns exhibit that middle rare earth elements are slightly enriched with weak positive anomalies for both Y (0.93~1.01) and Ce (0.97~1.15) and weak negative anomalies for Eu (0.87~0.99). The δ¹³C_PDB value of the ore ranges from −13.4‰ to −23.3‰, which is consistent with the δ¹³C_PDB value range of organic matter. Synthesizing these findings, it is concluded that the Qingshagou Mn deposit formed in a suboxic to oxic environment, the ore-forming materials were primarily derived from a submarine hydrothermal system, and the changes in redox conditions promoted the Mn precipitation. Full article

Honey is a natural food product which in traditional production represents a clear example of the “farm-to-table” principle, as it excludes any processing of the original product. This study proposes an analytical approach for determining 30 most frequently determined chemical elements (Ag, Al, As, B, Ba, Bi, Ca, Cd, Co, Cr, Cs, Cu, Ga, In, Fe, K, Li, Mg, Mn, Na, Ni, P, Pb, Rb, S, Se, Sr, Te, V, and Zn) in honey, emphasizing the use of a relatively large sample mass to overcome sample heterogeneity and ensure accurate and reliable results. About 31 linden and 16 rapeseed honey samples from different Bulgarian regions were analyzed. Pollen analysis data showed that pollen content ranged from 30 to 78% for linden and 30 to 93% for rapeseed honey. The results identify a group of elements—K, Ca, Mg, Sr, and Rb—whose concentrations show statistically significant dependence on the floral origin and purity of the honey. Based on these findings, these elements are proposed as potential markers for identifying the botanical origin of honey. Furthermore, macronutrients and micronutrients (P, S, B, Cu, Fe, Mn, and Zn), which are generally subject to homeostatic regulation, as well as micro-elements (Al, As, Cd, Co, Cr, and Pb), which are more strongly influenced by environmental factors, showed limited discriminatory potential and no clear correlation with floral purity and botanical origin. Therefore, they should not be used as criteria when assessing the botanical origin of honey, but rather as indicators of environmental pollution and potential quality or safety concerns. Overall, the research contributes to improving the reliability of botanical classification of honey by combining robust analytical methodology with statistically validated elemental markers, while also distinguishing between natural compositional features and contamination-related signals. Full article

This study evaluated the phytoremediation potential of the halophytic plant Sesuvium portulacastrum (L.) L. for treating industrial wastewater (IWW) in a hydroponic system over a nine-day exposure period. After treatment, the physicochemical analysis of IWW revealed a significant decrease in chemical oxygen demand (COD), biological oxygen demand (BOD), TSs (total solids), total dissolved solids (TDSs), TSSs (total suspended solids), ammonia, phosphate, and nitrate. The COD and BOD were reduced by 90.7% and 82.9%, respectively. The metal analysis indicated a significant decrease in Fe (95%), Mn (87.4%), and Al (93.9%) and complete removal of Ni, Pd, and Zn. The plant stress responses were assessed through the estimation of photosynthetic pigments (Chlorophyll-a, Chlorophyll-b, Total chlorophyll), phenolic and flavonoid contents, and antioxidant activity. Total chlorophyll declined from 1.449 mg/g (control) to 1.20 mg/g on Day 3, followed by partial recovery to 1.25 mg/g by Day 9, indicating physiological acclimatization. Total phenolic content reached 14 mg GAE/g in leaves and 12 mg GAE/g in stems on Day 6, while Total flavonoid content increased from ~70 µg/g (control) to 115 µg/g on in leaves. The metabolic profiling using GC-MS/MS revealed distinct time- and tissue-specific metabolic responses, with 53 metabolites identified in roots and 62 metabolites in leaves. The major differentially accumulated metabolites were sucrose, pinitol, talose and psicose, with peak accumulation at Day 6. A biphasic metabolic response pattern, characterized by early stress perception followed by adaptability, was observed. Phytotoxicity assays using Vigna radiata demonstrated improved germination from 15% (untreated IWW) to 95% after treatment. Overall, the study highlights the strong phytoremediation potential of halophyte S. portulacastrum as an environmentally friendly alternative for industrial wastewater remediation. Full article

This study proposes a novel synergistic design strategy to enhance the oxidation resistance of FeNiCuAl-based high-entropy alloys by integrating multi-element alloying (Cr-Co-Mn), trace Y modification, and laser-cladding-induced nanocrystallization. While the Base Alloy exhibited a mass gain of approximately 15 mg/cm² after oxidation at 900 °C for 120 h, the addition of Cr_2.5Co_2.5Mn_2.5 promoted the formation of a multilayered oxide scale (outer MnCr₂O₄/inner Al₂O₃), reducing the parabolic oxidation rate constant to 1.7 × 10⁻⁵ mg²·cm⁻⁴·s⁻¹. The originality of this work lies in the coupling of compositional and microstructural engineering; further addition of 0.5 at.% Y decreased this constant to 1.7 × 10⁻⁶ mg²·cm⁻⁴·s⁻¹—a three-order-of-magnitude reduction relative to the Base Alloy, while increasing the apparent oxidation activation energy to ~350 kJ/mol. After 100 thermal cycles at 1000 °C, the designed alloy showed a mass change of only 0.05 ± 0.02 mg/cm², with its critical load and interfacial fracture energy reaching 78 N and 14.8 J/m², respectively. Furthermore, the alloy retained a hardness of 310 HV, an elastic modulus of 135 GPa, and a tensile strength of 240 MPa at elevated temperature. These results demonstrate that the synergistic integration of chemical and structural optimization provides a new paradigm for designing low-cost, high-performance FeNiCuAl-based protective coatings. Full article

This work investigated the effect of yttrium addition on the pre-oxidation behavior of Fe–25Ni–20Cr–4Al–1Nb–1Mn–1.5Si-based alloys at 1000 °C in a 4% H₂ + 0.2% CH₄ + Ar + 0.25% H₂O atmosphere. The oxidation resistance and oxide scale adhesion were evaluated through cyclic oxidation tests and micro-scratch measurements. Results show that the Y-free alloy formed a discontinuous oxide layer, whereas all Y-containing alloys formed a continuous and dense Al₂O₃ scale. Incorporating 0.2 wt.% Y increased the work of adhesion by approximately 7 to 9 times relative to the Y-free sample, indicating a pronounced interfacial strengthening effect. The role of yttrium content and oxygen partial pressure in promoting alumina-scale formation was discussed based on thermodynamic considerations and microstructural evidence. Full article

The hydrogen embrittlement (HE) behavior of an Fe–18Mn–8Al–1C–5Ni lightweight steel containing a fine and uniformly distributed B2 phase and κ-carbide was investigated by slow strain rate tensile testing with in situ hydrogen charging. Hydrogen charging reduces the elongation from 28.2% to 11.2%, while preserving an ultimate tensile strength above 1100 MPa and yielding an HE index of 60.2%. A thermal desorption analysis reveals a multi-peak desorption curve corresponding to diffusible hydrogen, hydrogen reversibly trapped at κ-carbides, and hydrogen strongly bound at the B2/γ interfaces, revealing a hierarchical hydrogen trapping behavior. Electron backscatter diffraction and electron channeling contrast imaging analyses near the fracture head region further reveal that localized hydrogen enrichment at the B2/γ boundaries induces severe stress concentration and interfacial weakening, shifting the fracture mode from ductile micro-void coalescence in air to hydrogen assisted intergranular and interphase cracking. This study clarifies the distinct roles of coherent κ-carbide and B2/γ interfaces in hydrogen trapping and crack initiation, offering a microstructure-based perspective for designing high-strength, HE resistant lightweight steels. Full article

Large-scale disasters can result in chronic pollution of coastal environments with unanticipated and poorly quantified impacts, such as the reshaping of marine connectivity. A recent example is the collapse of the Fundão tailings dam in 2015, which released about 50 million m³ of mine waste into the Doce River, affecting one of Brazil’s largest estuarine–mangrove systems. Here, we combine a high-resolution CROCO hydrodynamic simulation with an individual-based Lagrangian model (Ichthyop) to track the dispersal of mangrove crab (Ucides cordatus) larvae from four estuaries along the southeastern Brazilian margin between 2022 and 2024. Trajectories crossing seasonal msPAF fields derived from in situ water-quality measurements were used to quantify larval exposure to contaminants from mine waste. These fields were based on measured concentrations of As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V, Zn, and Al. Results show that surface shelf flow and mesoscale activity in the vicinity of the Doce River mouth contribute to offshore export of larvae, while the reef-dominated Abrolhos shelf promotes retention. Interannual variability alternates between long-distance export and local retention, associated with regional climate variability. Larval mortality rates caused by offshore advection and lethal temperature are high (65–75%). In addition to these modeled mortality sources, surviving cohorts frequently crossed areas with elevated msPAF values during transport, indicating potential exposure to metal(loid) mixtures. This suggests that the regional connectivity of U. cordatus is under chronic stress that likely compromises the integrity and resilience of coastal populations, since southern estuaries depend strongly on northern larval sources. The integration of Lagrangian simulations with in situ contaminant monitoring and spatially explicit exposure metrics demonstrates that transport pathways regulate not only connectivity among estuaries but also the duration and intensity of larval exposure to pollutants. Full article