Search Results (33)

Background: There is growing interest in the potential role of manganese (Mn) in the development of Alzheimer’s Disease and related dementias (ADRD). Methods: In this nested pilot study of a ferroalloy worker cohort, we investigated the impact of chronic occupational Mn exposure on cognitive function through β-amyloid (Aβ) deposition and multi-omics profiling. We evaluated six male Mn-exposed workers (median age 63, exposure duration 31 years) and five historical controls (median age: 60 years), all of whom had undergone brain PET scans. Exposed individuals showed significantly higher Aβ deposition in exposed individuals (p < 0.05). The average annual cumulative respirable Mn was 329.23 ± 516.39 µg/m³ (geometric mean 118.59), and plasma Mn levels were significantly elevated in the exposed group (0.704 ± 0.2 ng/mL) compared to controls (0.397 ± 0.18 in controls). Results: LC-MS/MS-based pathway analyses revealed disruptions in olfactory signaling, mitochondrial fatty acid β-oxidation, biogenic amine synthesis, transmembrane transport, and choline metabolism. Simoa analysis showed notable alterations in ADRD-related plasma biomarkers. Protein microarray revealed significant differences (p < 0.05) in antibodies targeting neuronal and autoimmune proteins, including Aβ (25–35), GFAP, serotonin, NOVA1, and Siglec-1/CD169. Conclusion: These findings suggest Mn exposure is associated with neurodegenerative biomarker alterations and disrupted biological pathways relevant to cognitive decline. Full article

Arsenic (As) and cadmium (Cd) contamination in groundwater poses significant risks to human health and environmental sustainability. Iron–manganese minerals and associated microorganisms in subsurface environments exhibit remarkable potential for immobilizing and transforming toxic metal(loid)s through adsorption, redox reactions, and co-precipitation. This study integrates bibliometric analysis with mechanistic review strategies to systematically evaluate the roles of iron–manganese biomineralization in As/Cd stabilization. Bibliometric insights identify emerging research trends, including the application of biogenic oxides and microbial redox cycles in groundwater remediation. Mechanistic analysis reveals how microbial–mineral interactions regulate As/Cd sequestration, emphasizing the influence of environmental factors such as pH, redox conditions, and microbial metabolic pathways. Case studies demonstrate the viability of in situ remediation technologies leveraging these biogeochemical processes, though challenges persist in achieving consistent field-scale performance and long-term stability. Future efforts should prioritize optimizing microbial consortia, advancing real-time monitoring systems, and integrating biogeochemical strategies with engineered barriers. By synthesizing quantitative trends and mechanistic principles, this work provides actionable frameworks for enhancing natural attenuation and designing sustainable remediation systems for metal-contaminated groundwater. Full article

Silicon (Si) is one of the biogenic elements in lake aquatic ecosystems. Sediments are both sinks and sources of Si, but little is known about its influence on the biogeochemical cycle of Si in lakes and its relationship to other biogenic factors such as carbon and nitrogen. Examining Caohai Lake, a typical macrophytic lake in China, this study systematically examined the different Si forms and biogenic silica (BSi) distribution characteristics and their coupling relationships with total organic carbon (TOC) and total nitrogen (TN) in surface sediments. Iron–manganese-oxide-bonded silicon (IMOF-Si) and organic sulfide-bonded silicon (OSF-Si) jointly accounted for 95.9% of Valid-Si in the sediments, indicating that the fixation of Si by organic matter and iron–manganese oxides was the main mechanism underlying the formation of the different forms of Valid-Si in sediments. The release and recycling of Si in sediments may be mainly driven by mineralized degradation of organic matter and anoxic reduction conditions at the sediment–water interface. The content of biogenic Si (BSi) in the sediments was relatively higher in the southern and eastern areas, which could be explained by the intensification of eutrophication and the increased abundance of diatomaceous siliceous organisms in these areas seen in recent years. The TOC and TN contents in the sediments were generally high, and the sources of organic matter in the sediments included both the residues of endophytes (main contributors) and the input of terrigenous organic matter. TOC and TN both had highly significant correlations with OSF-Si and Valid-Si, which demonstrated that Valid-Si had excellent coupling relationships with C and N in the sediments. The good correlation between BSi, TOC and TN (p < 0.01), as well as the high C/Si, N/Si mole ratio of TOC and TN to BSi, respectivelny, indicating that the dissolution and release rate of BSi may be much higher than the degradation rate of organic matter from the sediments, especially in the areas with a higher abundance of siliceous organisms. Full article

Silicon (Si) is one of the main biogenic elements in the aquatic ecosystem of lakes, significantly affecting the primary productivity of lakes. Lake sediment is an important sink of Si, which exists in different Si forms and will be released and participate in the recycling of Si when the sediment environment changes. Compared to carbon (C), nitrogen (N) and phosphorus (P), the understanding of different Si forms in sediments and their biogeochemical cycling is currently insufficient. Dianchi Lake, a typical eutrophic lake in southwest China, was selected as an example, and the contents of different Si forms and biogenic silicon (BSi), as well as their correlations with total organic carbon (TOC), total nitrogen (TN), and chlorophyll a in the surface sediments, were systematically investigated to explore Si’s recycling characteristics. The results showed that the coupling relationship of the four different Si forms in the surface sediments of Dianchi Lake was poor (p > 0.05), indicating that their sources were relatively independent. Moreover, their formation may be greatly influenced by the adsorption, fixation and redistribution of dissolved silicon by different lake substances. The contents of different Si forms in the surface sediments of Dianchi Lake were ranked as iron-manganese-oxide-bonded silicon (IMOF-Si) > organic sulfide-bonded silicon (OSF-Si) > ion-exchangeable silicon (IEF-Si) > carbonate-bound silicon (CF-Si). In particular, the contents of IMOF-Si and OSF-Si reached 2983.7~3434.7 mg/kg and 1067.6~1324.3 mg/kg, respectively, suggesting that the release and recycling of Si in surface sediments may be more sensitive to changes in redox conditions at the sediment–water interface, which become the main pathway for Si recycling, and the slow degradation of organic matter rich in OSF-Si may lead to long-term and continuous endogenous Si recycling. The low proportion (0.3~0.6%) and spatial differences of biogenic silicon (BSi) in the surface sediments of Dianchi Lake, as well as the poor correlation between BSi and TOC, TN, and chlorophyll a, indicated that the primary productivity of Dianchi Lake was still dominated by cyanobacteria and other algal blooms, while the relative abundance of siliceous organisms such as diatoms was low and closer to the central area of Dianchi Lake. Additionally, BSi may have a faster release capability relative to TOC and may participate in Si recycling. Full article

A fungus, Acremonium strictum KR21-2, produces biogenic manganese oxides (BMOs) that can oxidize exogenous Mn²⁺ ions to form different BMO phases. When other guest ions are present during the BMO formation, it can strongly affect the mineralogical characteristics of the resultant BMO phase. The impact of coexisting Ni²⁺ ions on the mineralogy of BMO phases formed through enzymatic Mn(II) oxidation and its sequestration ability is not yet fully understood. To better understand it, repeated sequestration experiments were conducted using BMOs in Ni²⁺/Mn²⁺ binary, single Ni², and single Mn²⁺ solution systems with a pH range of 6.0 to 7.5. It was observed that simultaneous sequestration of Ni²⁺ and Mn²⁺ was efficient, with irreversible Ni²⁺ incorporation at pH values above 7.0. The resultant BMO phases showed that Ni²⁺-bearing Mn oxides resembling feitknechitite (β-MnOOH) were developed through enzymatic Mn(II) oxidation. At pH values below 6.5, the turbostratic birnessite structure was maintained even in Ni²⁺/Mn²⁺ binary solutions, and subsequently, the Ni²⁺ sequestration efficiency was low. The pseudo-first-order rate constants of enzymatically inactivated BMOs for Mn²⁺ sequestration were two orders of magnitude lower than those of active BMOs, indicating the crucial role of the enzymes in precipitating Ni²⁺-bearing Mn oxide phases. These findings provide new insights into the mechanism of Ni²⁺ interaction with Mn oxide through microbial activity under circumneutral pH conditions. Full article

Manganese oxides reportedly exhibit pronounced adsorption capacities for numerous heavy-metal ions owing to their unique structural properties. Herein, a biogenic manganese oxide (BMO) composite was developed and used to remove Ni ions from Ni²⁺-containing electroplating wastewater. The formation of BMO and the micro-/nanoscale fine microstructure were characterized via scanning/high-resolution transmission electron microscopies and X-ray diffraction assays. Under the optimized conditions, with an adsorption temperature of 50 °C, pH 6, the BMO composite showed a 100% removal efficiency within a rapid equilibrium reaction time of 20 min towards an initial Ni²⁺ concentration of 10 mg L⁻¹ and a remarkable removal capacity of 416.2 mg g⁻¹ towards an initial Ni²⁺ concentration of 600 mg L⁻¹ in Ni-electroplating wastewater. The pseudo-second-order equation was applicable to sorption data at low initial Ni²⁺ concentrations of 10–50 mg L⁻¹ over the time course. Moreover, Freundlich isotherm models fitted the biosorption equilibrium data well. Fourier-transform infrared spectroscopic analysis validated that the removal capacity of the BMO composite was closely associated with structural groups. In five continuous cycles of adsorption/desorption, the BMO composite exhibited high Ni²⁺ removal and recovery capacities, thereby showing an efficient and continuous performance potential in treating Ni²⁺-containing industrial wastewater. Full article

Mn-oxidizing microorganisms oxidize environmental Mn(II), producing Mn(IV) oxides. Pseudomonas putida MnB1 is a widely studied organism for the oxidation of manganese(II) to manganese(IV) by a multi-copper oxidase. The biogenic manganese oxides (BMOs) produced by MnB1 and similar organisms have unique properties compared to non-biological manganese oxides. Along with an amorphous, poorly crystalline structure, previous studies have indicated that BMOs have high surface areas and high reactivities. It is also known that abiotic Mn oxides promote oxidation of organics and have been studied for their water oxidation catalytic function. MnB1 was grown and maintained and subsequently transferred to culturing media containing manganese(II) salts to observe the oxidation of manganese(II) to manganese(IV). The structures and compositions of these manganese(IV) oxides were characterized using scanning electron microscopy, energy dispersive X-ray spectroscopy, inductively coupled plasma optical emission spectroscopy, and powder X-ray diffraction, and their properties were assessed regarding catalytic functionality towards water oxidation in comparison to abiotic acid birnessite. Water oxidation was accomplished through the whole-cell catalysis of MnB1, the results for which compare favorably to the water-oxidizing ability of abiotic Mn(IV) oxides. Full article

The compositions of metalliferous sediments associated with hydrothermal vents can provide key geochemical data for locating seafloor sulfides. In this study, we present the geochemistry of seabed sediments from the Xunmei hydrothermal field (HF) in the South Mid-Atlantic Ridge (SMAR). The results indicate that the sediments are mainly composed of pelagic material (biogenic calcium components), basaltic debris, iron-manganese oxides, and hydrothermal components. The sediments are significantly enriched in Cu, Zn, Fe, and Co deriving from hydrothermal fluids, as well as Mn, V, Mo, U, and P, which are primarily scavenged from seawater. The northeastern Xunmei has the highest concentrations of Cu and Zn, while the northeastern, northern, and southern regions are characterized by great inputs of Fe. Manganese and Mo are mainly enriched in the western and southern parts and show a strong positive correlation, indicating that Mo is mainly scavenged by Mn oxides. Uranium, P, and Fe exhibit strong positive correlations, suggesting that they coprecipitate with Fe from hydrothermal plumes. Vanadium and Co are introduced into sediments in different ways: V is scavenged and coprecipitated by hydrothermal plumes, and Co is derived from sulfide debris. Based on the contents of Cu and Zn and Cu/Fe (0.159), Zn/Fe (0.158), and Fe/Mn (1440) ratios, it can be inferred that a high-temperature hydrothermal vent existed in northeastern Xunmei. In combination with the distribution patterns of the above elements, the hydrothermal vents in the southern part ceased erupting after a short period of activity. In addition, the high Mn anomaly and the high U/Fe ratios at the boundaries of the investigated area indicate the presence of a relatively oxidized environment in southwestern Xunmei. Full article

Green synthesis offers a superior alternative to traditional methods for producing metal and metal oxide nanoparticles. This approach is not only benign and safe but also cost-effective, scalable, and straightforward, operating under ambient conditions. Notable metals and metal oxide nanoparticles, such as manganese oxides, iron oxides, silver, and gold, have been produced using various bio-reductants derived from plant extracts. These biological agents not only expedite the reduction process but also stabilize the nanoparticles, serving dual roles as reducing and capping agents. This review presents the green synthesis of nanoparticles (NPs) obtained from biogenic wastes and plant extracts. The green-synthesized nanostructured MnO₂ nanoparticles are evaluated as a potential photocatalyst for water treatment and as an electrode material in lithium-ion batteries and supercapacitors. The green-derived iron oxide nanoparticles are examined as promising antioxidant, anti-inflammatory, and anti-diabetic agents. Additionally, this review discusses the green synthesis of precious metal nanoparticles, specifically silver (Ag NPs) and gold (Au NPs), highlighting their potential medical applications in areas like antiviral treatments and cancer therapy. Full article

We carried out a comprehensive study of native gold (morphology, composition, intergrowths, and microinclusions) from alluvial deposits of the Kamenny stream (Ozerninsky ore cluster, Western Transbaikalia, Russia). The study showed that there were four types of native gold, which differed significantly in their characteristics and probably had different primary sources from which placers were formed: gold–quartz, oxidized gold–sulfide, gold–silver, and zones of listvenites with copper–gold and gold–brannerite (Elkon-type). Particular attention was paid to the study of unique, both in size and in composition, gold–brannerite nuggets of the Kamenny stream. It was established that the gold in the gold–brannerite nuggets (GBNs) had wide variations in chemical composition and mineral features. According to them, there were five different fineness types of native gold: 750–800‰; 850–880‰; 880–920‰; 930–960‰; and 980–1000‰. The data obtained indicated a multistage, possibly polygenic, and probably polychronous formation of GBN gold–uranium mineralization. The first stage was the formation of early quartz–nasturanium–gold–W–rutile–magnetite association (Middle–Late Paleozoic age). The second was the crystallization of brannerite and the replacement of an earlier pitchblende with brannerite (Late Triassic (T3)–Early Jurassic (J1) age). The third was the formation of the hematite–barite–rutile–gold association as a result of deformation–hydrothermal processes, which was associated with the appearance of zones of alteration in brannerite in contact with native gold with 8–15 wt.% Ag. The fourth was hypergene or the low-temperature hydrothermal alteration of minerals of early stages with the development of iron hydroxides (goethite) with impurities of manganese, tellurium, arsenic, phosphorus, and other elements. The carbon isotopic composition of an organic substance indicates the involvement of a biogenic carbon source. In the OOC area, there were signs that the composition of the GBNs and the quartz–chlorite–K–feldspar-containing rocks corresponded to Elkon-type deposits. Full article

Many regions of the United States contain manganese deposits economically valuable in New England, Appalachian, and Piedmont regions in the Eastern United States, in Northern Arkansas, and, to a small extent, in Central–Western California. Mn oxide/hydroxide (commonly referred to as Mn oxide minerals) are found in a wide variety of geological settings and occur as fine-grained aggregates, veins, marine and freshwater nodules and concretions, crusts, dendrites, and coatings on rock surfaces (e.g., desert varnish). How manganese oxides form and what mechanisms determine which oxides are likely to form are limited and still debated. This paper focuses on Mn oxides collected at the southern bound of the abandoned open-pit site called Crimora Mine (Augusta County, Virginia). This study uses mineralogical and chemical features to shed light on the origin of manganese deposits in Crimora along the western foot of the Blue Ridge in South–West Virginia. We report the first detailed study on the genesis of the Crimora manganese deposit conducted since the mine was closed in the 1950s. Crimora Mine sample is dark black fine- to medium-grained round and oblong nodules coated with a fine-grained intermix of yellowish earthy limonite, clays, and quartz. Scanning electron microscopy (SEM) revealed that the Crimora Mn-oxides exhibit concentric layering, breccia-like matrices, and veins. X-ray powder diffraction (XRPD) identified the set of Mn minerals as hollandite and birnessite. The concentration and range of dissolved chemical species in freshwater, seawater, and hydrothermal depositional fluids impart a geochemical signature to the Mn-oxides, providing a diagnostic tool to shed light on their genetic origin. Inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis of the Crimora manganese oxides shows Mn, Fe, and Ti, as well as trace elements such as Co, Ba, Y, Zn, Cr, Ni, Tl, La, V, and Li. A bivariate analysis based on the geochemical correlation of Mn and other common substituting cations (e.g., Fe, Co, Ti) shows a mixed genesis in different environments with varying biological and sedimentary supergene (freshwater and marine) conditions. These data suggest that the Mn-rich deposit in Crimora, VA, was formed in a continental margin environment of surficial deposits and reprecipitated in mixed biogenic and supergene conditions. Full article

Temperature is an important factor influencing the treatment effect of biological aerated filters (BAFs). In this study, BAFs incorporating biological manganese oxides (BMOs) were used to treat micro-polluted source water containing organic masses and ammonia, and the influence of temperature on the removal efficiency of the pollutants was investigated. The results showed that after the formation of biogenic manganese oxides (BMOs) in the filter layer, the removal efficiency of CODMn significantly improved. When the water temperature was approximately 24 °C, 16 °C, and 6~8 °C, the removal rates of COD_Mn, ammonia, and manganese were 60.64, 42.55, and 20.48; 98.40, 95.58, and 85.04; and 98.70, 97.63, and 96.38%, respectively. The influence of water temperature on the removal efficiency of the pollutants was hierarchically structured as follows: COD_Mn > ammonia > manganese. Analysis of the removal efficiencies of the pollutants along the filter layer showed that COD_Mn had been eliminated in every filtration layer, and ammonia and manganese were mainly removed in the 0~0.4 m and 0~0.8 m regions of the filter layer, respectively. With a decreasing water temperature, the concentrations of COD_Mn, ammonia, and manganese along the filter layer increased. The biological COD_Mn, manganese, and ammonia removal processes were all first-order kinetic reactions. With a decreasing water temperature, the kinetic constant k gradually decreased, and the reaction half-life (t_1/2) gradually increased. Full article

Filamentous manganese (Mn) oxide particles, which occur in the suboxic zone of stratified waterbodies, are important drivers of diverse elemental cycles. These particles are considered to be bacteriogenic; despite the importance of biogeochemical implications, however, the environmental factor responsible for their formation has not been identified. The aim of this study was to demonstrate the involvement of algal extracellular polysaccharides in Mn oxide particle formation. Based on this study of laboratory cultures of a model Mn(II)-oxidizing bacterium, the supply of algal extracellular mucilage was shown to stimulate Mn(II) oxidation and thus the production of filamentous Mn oxide particles. This observation was consistent with the results obtained for naturally occurring particles collected from a near-bottom layer (depth of approximately 90 m) in the northern basin of Lake Biwa, Japan, that is, most Mn particles resembling δ-MnO₂ were associated with an extracellular mucilage-like gelatinous matrix, which contained dead algal cells and was lectin-stainable. In the lake water column, polysaccharides produced by algal photosynthesis sank to the bottom layer. The analysis of the quality of water samples, which have been collected from the study site for 18 years, reveals that the annual average total phytoplankton biovolume in the surface layer correlates with the density of filamentous Mn particles in the near-bottom layer. Among different phytoplankton species, green algae appeared to be the key species. The results of this study suggest that algal extracellular polysaccharides serve as an important inducer for the formation of filamentous Mn oxide particles in the near-bottom layer of the northern basin of Lake Biwa. Full article

Manganese oxides are considered an essential component of natural geochemical barriers due to their redox and sorptive reactivity towards essential and potentially toxic trace elements. Despite the perception that they are in a relatively stable phase, microorganisms can actively alter the prevailing conditions in their microenvironment and initiate the dissolution of minerals, a process that is governed by various direct (enzymatic) or indirect mechanisms. Microorganisms are also capable of precipitating the bioavailable manganese ions via redox transformations into biogenic minerals, including manganese oxides (e.g., low-crystalline birnessite) or oxalates. Microbially mediated transformation influences the (bio)geochemistry of manganese and also the environmental chemistry of elements intimately associated with its oxides. Therefore, the biodeterioration of manganese-bearing phases and the subsequent biologically induced precipitation of new biogenic minerals may inevitably and severely impact the environment. This review highlights and discusses the role of microbially induced or catalyzed processes that affect the transformation of manganese oxides in the environment as relevant to the function of geochemical barriers. Full article

Radium isotopes have traditionally been used as tracers of surface and underground fresh waters in land–ocean interactions. The concentration of these isotopes is most effective on sorbents containing mixed oxides of manganese. During the 116 RV Professor Vodyanitsky cruise (22 April–17 May 2021), a study about the possibility and efficiency of ²²⁶Ra and ²²⁸Ra recovery from seawater using various types of sorbents was conducted. The influence of seawater flow rate on the sorption of ²²⁶Ra and ²²⁸Ra isotopes was estimated. It was indicated that the Modix, DMM, PAN-MnO₂, and CRM-Sr sorbents show the best sorption efficiency at a flow rate of 4–8 column volumes per minute. Additionally, the distribution of biogenic elements (dissolved inorganic phosphorus (DIP), silicic acid, and the sum of nitrates and nitrites), salinity, and ²²⁶Ra and ²²⁸Ra isotopes was studied in the surface layer of the Black Sea in April–May 2021. Correlation dependencies between the concentration of long-lived radium isotopes and salinity are defined for various areas of the Black Sea. Two processes control the dependence of radium isotope concentration on salinity: conservative mixing of riverine and marine end members and desorption of long-lived radium isotopes when river particulate matter meets saline seawater. Despite the high long-lived radium isotope concentration in freshwater in comparison with that in seawater, their content near the Caucasus shore is lower mainly because riverine waters meet with a great open seawater body with a low content of these radionuclides, and radium desorption processes take place in an offshore area. The ²²⁸Ra/²²⁶Ra ratio derived from our data displays freshwater inflow spreading over not only the coastal region, but also the deep-sea region. The lowered concentration of the main biogenic elements corresponds to high-temperature fields because of their intensive uptake by phytoplankton. Therefore, nutrients coupled with long-lived radium isotopes trace the hydrological and biogeochemical peculiarities of the studied region. Full article