Search Results (16)

This study focuses on the synthesis and characterization of a cationic ion-exchange sorbent derived from vermiculite and epoxy acrylate copolymers, designed to address freshwater scarcity by removing toxic metal ions from aqueous environments. The sorbent was engineered to preserve the chemical integrity of freshwater while adhering to environmental safety standards. Vermiculite served as the base material, modified with glycidyl methacrylate (GMA), acrylonitrile (ACN), and orthophosphoric acid (H₃PO₄) in a mass ratio of 1:0.35:0.15:3. Optimization experiments explored varying H₃PO₄ proportions (two- and threefold increases) to refine the synthesis conditions. The materials underwent microwave irradiation at 300 W for 10 min. Infrared (IR) spectroscopy confirmed the presence of functional groups (P=O, P−O−C), enhancing sorption capacity, while scanning electron microscopy (SEM) revealed a porous structure crucial for adsorption. Sorption properties, assessed via atomic emission spectroscopy, demonstrated capacities of 39.80 mg/g for MoO₄²⁻ and 39.06 mg/g for ReO₄⁻, with extraction efficiencies of 79% and 78%, respectively. Chemical stability tests indicated the sorbent retained up to 90% of its functionality in aggressive environments, highlighting its robustness. The developed sorbent offers a high-performance, cost-effective solution for heavy metal removal from wastewater, advancing sustainable water purification technologies. Full article

The European Food Safety Authority (EFSA) monitors the presence and concentration of contaminants in food to mitigate health risks. EU legislation sets maximum levels of heavy metals in foods, including cadmium (Cd), lead (Pb), and total Hg (THg) in seafood, due to their toxicity. In the framework of official control, between 2014 and 2023, 5854 seafood samples were collected and 4300 analyses for THg, 3338 for Cd, and 2171 for Pb were performed using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and cold vapor atomic absorption spectrometry (CVAAS). The aim was to assess the proportion of contaminated foods in the dataset, the concentration of contaminants, and the potential health risks associated with their intake. Of the total samples analyzed, 142 (2.43%) were found to be non-compliant (n.c.). Concentrations exceeding the limits for Cd were primarily detected in cephalopods (n = 17), mainly squids. In contrast, Hg levels exceeded the limits in marine fish (n = 118), notably in swordfish (11.30% of n.c. samples among those analyzed for this species), sharks (6.48%), and tuna species (3.11%). Regarding Pb, only a single bivalve sample was found to exceed the maximum limits. A preliminary assessment of weekly exposure to Hg through swordfish consumption raised concerns about the frequent intake of marine top predators, particularly for vulnerable people. Full article

The present study aimed to assess the pollution of Bulgarian brackish lakes based on their ability to accumulate the heavy metals Cd, Zn and Ni. Physicochemical parameters, including pH, electrical conductivity and salinity of the waters, were determined by potentiometric methods. The heavy metal content of the water and crustacean samples was determined by atomic absorption spectrophotometry. The highest pH in the investigated lakes (Atanasovsko Lake, Poda and Pomorie Lake) in the period May–September 2021 was found in the month of September, in the waters of Atanasovsko Lake (8.84). The concentrations of Cd measured in Atanasovsko Lake in the fall were in the order of 0.0125 µg/L—the highest value recorded for all the studied water bodies. The concentrations of zinc and nickel in the waters did not exceed the norms in Bulgarian legislation. The dynamics of biogenic elements (Zn and Ni) in crustaceans were inversely proportional to those found in the waters. The levels of the toxicant cadmium as well as the metals zinc and nickel in the species Gammarus spp. and Atremia spp., inhabiting all analyzed water bodies, were significantly lower than those specified in the Bulgarian and European legislation. The pH and electrical conductivity parameters of the tested waters, as well as the concentrations of the heavy metals, cadmium, zinc and nickel, were within the recommended values. High positive correlations were determined between the content of nickel, on the one hand, and cadmium and zinc, on the other, in the organism of the investigated crustaceans. A longer period of research is needed to accurately determine the degree of contamination of these waters. Full article

With the growing population, industrialization, and agriculture, water contamination not only affects people but entire ecosystems. Metal–organic frameworks (MOFs), because of their large surface area and porosity, show great potential as adsorbents for removing pollutants, such as heavy metals, from contaminated water. The current research aims at examining copper (II) benzene-1,3,5-tricarboxylate (Cu-BTC) MOFs and understanding the mechanism for their adsorption of Pb(II) from aqueous solution. The Cu-BTC samples were characterized using FTIR and XRD, and their surface area and porosity were determined based on N₂ adsorption isotherms. The concentration of Pb(II) in the solutions was measured using atomic absorption spectroscopy (AAS). Both kinetic and equilibrium adsorption data were collected and then analyzed using numerical models. The analyses led to the findings that the limiting steps in the adsorption of Pb(II) on Cu-BTC are (a) pore diffusion of Pb(II) and (b) the availability of the active sites on Cu-BTC MOFs. It was further revealed that the former step is more dominant in the adsorption of Pb(II) when the lead concentration is low. The latter step, which is directly proportional to the surface areas of the MOFs, affects the adsorption to a greater extent when the lead concentration is high. The results also show that adsorption of Pb(II) ions on Cu-BTC is mainly a multi-layer heterogeneous process. Full article

Amyloid fibrillation of α-synuclein is implicated in the pathogenesis of Parkinson’s disease and heavy metal ions such as Fe³⁺, Zn²⁺, and Cu²⁺ are known to be involved in the process. In this work, we explored the use of FTIR spectroscopy to look into the modulation effects of Fe³⁺, Zn²⁺, and Cu²⁺ on the amyloid fibrillation of α-synuclein. We performed a curve-fitting analysis on the FTIR amide I bands of these α-synuclein fibril systems, namely, the pristine fibril and the fibrils prepared in the presence of Fe³⁺, Zn²⁺, and Cu²⁺. We found that the α-synuclein fibrils under the influences of metal ions all possessed a parallel β-sheet structure, turn structure, and disordered structure, similar to that of pristine α-synuclein fibril. We also observed metal-induced increases in the proportions of the β-sheet secondary structure within the α-synuclein fibrils, with Fe³⁺ being the most effective inducer. We performed second derivative analysis of the side chain carboxylic groups of α-synuclein fibrils and found that the side chain microenvironment of the α-synuclein fibrils was more influenced by Fe³⁺ than Zn²⁺, and Cu²⁺. In addition, our atomic force microscopic study revealed that the morphologies of α-synuclein fibrils under the influence of Fe³⁺ was quite different from that of the Zn²⁺ and Cu²⁺ systems. Our FTIR results suggested that the modulation effects of Fe³⁺, Zn²⁺, and Cu²⁺ on α-synuclein fibrillation occurred at both secondary and quaternary structural levels. At last, we proposed a mechanistic hypothesis to interpret how metal ions could affect the morphology of α-synuclein amyloid fibril based on the conformational plasticity properties of intrinsically disordered proteins. Full article

In this study, the asphaltene extracted from Luntai heavy oil was oxidized by a mixture of propionic anhydride and hydrogen peroxide without and with a catalyst. Elemental analysis and infrared spectroscopy results indicated the occurrence of oxygen addition, condensation, and side chain cleavage reactions in the oxidation process. Oxidation products were divided into methanol solubles and methanol insolubles. The H/C and O/C atomic ratios of the MeOHS in the oxidation products without a catalyst were higher than those of the Luntai asphaltene. MeOHS had fewer aromatic rings than Luntai asphaltene. Compared with the oxidative reaction without a catalyst, the total mass of oxidation products and the proportion of MeOHS in oxidation products both increased after catalytic oxidation. This low-temperature oxidation technology can be used to upgrade asphaltenes, and thus can promote the exploitation and processing of heavy oil. Full article

Heavy metal ions and organic pollutants often coexist in industrial effluents. In this work, silica-di-block polymer hybrids (SiO₂-g-PBA-b-PDMAEMA) with two ratios (SiO₂/BA/DMAEMA = 1/50/250 and 1/60/240) were designed and prepared for the simultaneous removal of Cr(VI) and phenol via a surface-initiated atom-transfer radical polymerization process using butyl methacrylate (BA) as a hydrophobic monomer and 2-(Dimethylamino)ethylmethacrylate (DMAEMA) as a hydrophilic monomer. The removal efficiency of Cr(VI) and phenol by the hybrids reached 88.25% and 88.17%, respectively. The sample with a larger proportion of hydrophilic PDMAEMA showed better adsorption of Cr(VI), and the sample with a larger proportion of hydrophobic PBA showed better adsorption of phenol. In binary systems, the presence of Cr(VI) inhibited the adsorption of phenol, yet the presence of phenol had a negligible effect on the adsorption of Cr(VI). Kinetics studies showed that the adsorption of Cr(VI) and phenol fitted the pseudo-second-order model well. Thermodynamic studies showed that the adsorption behavior of Cr(VI) and phenol were better described by the Langmuir adsorption isotherm equation, and the adsorption of Cr(VI) and phenol were all spontaneous adsorptions driven by enthalpy. The adsorbent still possessed good adsorption capacity for Cr(VI) and phenol after six adsorption–desorption cycles. These findings show that SiO₂-g-PBA-b-PDMAEMA hybrids represent a satisfying adsorption material for the simultaneous removal of heavy metal ions and organic pollutants. Full article

The geopolymerization process is an appropriate way of disposing of municipal solid waste incineration fly ash (MSWIFA), and possesses the advantages of immobilizing the heavy metals and making full use of its pozzolanic properties in manufacturing green, cementitious materials. In this study, coal fly ash (FA) and metakaolin (MK) were used to prepare a geopolymer composite, with MK partially replaced by different proportions of MSWIFA through the alkali-activation method. The microstructure and hydration mechanism of the geopolymer composites containing MSWIFA were investigated through mercury intrusion porosimetry (MIP), scanning electron microscopy (SEM), and Fourier transform-infrared spectroscopy (FT-IR) tests; and the immobilization effect of the geopolymer paste on heavy metal ions was explored through inductively coupled plasma-atomic emission spectrometry (ICP-AES). The MIP analysis showed that the addition of MFARR had an overall degrading effect on the pore structure of the matrix. When the content of MSWIFA reached the maximum of 35%, the porosity and average pore diameter increased by 25% and 16%, respectively, corresponding to the case without MSWIFA. However, the pore size distribution exhibited an improving trend when the MFARR was increased from 15% to 25%. The SEM images revealed that the integrity of the micromorphology of the geopolymer mortar became weaker after adding MSWIFA. When the MSWIFA content was increased to 35%, the microstructural compactness decreased and more pores and microcracks appeared in the matrix. The FT-IR pattern study suggested that all the geopolymer composites had a similar internal structure, consisting of O-H, C-O, Si-O-Si, and Si-O-Al. The main component of the geopolymer paste hydrated at 28 d remained dominated by calcium silica-aluminate (C-A-S-H), when the MSWIFA ranged from 0% to 35%. Finally, the ICP-AES results showed that the leaching concentrations of the geopolymer paste of J-40 at 28 d for Cd, Cr, Cu, Pb, and Zn met the requirements of Chinese standards. Full article

High lead–tin bronze is widely used in the selection of wear-resistant parts such as bearings, bearing bushes, aerospace pump rotors, turbines, and guide plates because of its excellent wear resistance, thermal conductivity, fatigue resistance, and strong load-bearing capacity. At present, high lead–tin bronze is used as a material for bimetal cylinders, which cannot meet the requirements of high-strength, anti-wear in actual working conditions under high temperature, high speed, and heavy load conditions, and is prone to de-cylinder, cylinder holding, copper sticking, etc. The reason for the failure of cylinder body parts is that the strength of copper alloy materials is insufficient, the proportion of lead in the structure is serious, and the wear resistance of the material is reduced. Therefore, it has important theoretical significance and application value to carry out research on the comprehensive properties of high-performance lead–tin bronze materials and reveal the strengthening and toughening mechanism. In this paper, The ZCuPb20Sn5 alloy is taken as the main research object, and the particle size, microstructure, mechanical properties, and friction of lead particles in ZCuPb20Sn5 alloy are systematically studied after single addition of B in ZCuPb20Sn5 alloy liquid. This paper takes ZCuPb20Sn5 alloy as the research object to study the effect of adding B on the morphology, microstructure, mechanical properties, and friction and wear properties of ZCuPb20Sn5 alloy lead particles, and discusses the strengthening and toughening mechanism of ZCuPb20Sn5 alloy under the action of B, and prepares a double high-performance lead–tin bronze alloy for metal cylinders. The main research results are as follows: The addition of B elements has an obvious refining effect on the α (Cu) equiaxed grains and lead particles in ZCuPb20Sn5 alloy. The average size of lead particles decreases from 30.0 µm to 24.8 µm as the B content increases from 0 wt.% to 0.1 wt.%. The reason for grain refinement is that B is easily concentrated at the grain boundary during the ZCuPb20Sn5 alloy solidification process, which affects the diffusion of solute atoms at the solidification interface, inhibits the grain growth, refines the grain, and hinders the sinking and homogenizes distribution between dendrites of lead; the tensile strength of the ZCuPb20Sn5 alloy improves. Relatively without B, when the addition of P is 0.1 wt.%, the tensile strength is the largest at 244.04 MPa, which enhances 13%; the maximum hardness gets 75.0 HB, which enhances 13.6%, as well as elongation get the maximum value at 17.2%. The main mechanism is that the addition of B forms a high melting point submicron Ni₄B₃ phase in the lead–tin bronze alloy. The Ni₄B₃ phase is dispersed in the matrix and strengthens the matrix. With the increase in B content (more than 0.1 wt.%), the Ni₄B₃ phase changes from sub-micron degree granular to micron degree block-like, and some defects such as shrinkage and porosity appear in the structure, resulting in a decrease in mechanical properties. Full article

Nowadays, the sorption-oriented approach is on the agenda in the remediation practices of lands contaminated with heavy metals. The current growing quantity of research accounts for different sorbents. However, there is still a lack of studies utilizing the economic criteria. Therefore, to ensure a wide application of opportunities, one of the necessary requirements is their economic efficiency in use. By utilizing these criteria, this manuscript researches the generally accepted natural sorbents for the assessment of heavy metal ions’ adsorption, such as peat, diatomite, vermiculite and their mixtures in different proportions and physical shapes. The methodological base of the study consists of the volumetric (titrimetric) method, X-ray fluorescence spectrometry and atomic absorption spectrometry. Experimental tests show a certain decline in the efficiency of heavy metal ions’ adsorption from aqueous salt solutes as follows: granular peat–diatomite > large-fraction vermiculite > medium-fraction vermiculite > non-granular peat–diatomite > diatomite. Full article

Humin is the waste residue from the process of preparing humic acid, which accounts for a large proportion of the raw material (weathered coal humic acid). Its Cd(II) adsorption performance is far inferior to that of humic acid. How to regenerate humin is of great significance to the low-cost treatment of Cd(II) pollution in wastewater. In this study, humin was modified by hyperbranched polyethyleneimine to enhance the adsorption capacity for Cd(II). Fourier transform infrared spectroscopy and the X-ray photoelectron spectrometer showed that hyperbranched polyethyleneimine was grafted to the surface of humin. Flame atomic absorption spectroscopy showed that the saturated Cd(II) adsorption capacity of the modified humin was increased to 11.975 mg/g, which is about 5 times than that of humin and is also higher than that of humic acid. The adsorption kinetics, adsorption isotherm, and thermodynamic properties of humic acid, humin, and modified humin were also studied. This study may provide a foundation for research utilizing natural resources to reduce heavy metal pollution in the environment. Full article

The symbiotic association between the roots of a plant and the mycelium of some fungi is identified as mycorrhizae. Symbiosis helps the plant to obtain nutrients from the soil more efficiently, and may favor the phytoremediation capacity of plants such as Lolium perenne, in soils contaminated with mercury. In this study, the morphological and molecular response was evaluated, as well as the variation in mercury accumulation in the different structures of L. perenne when associated with arbuscular mycorrhizal fungi. Association tests were performed to determine the optimal concentration of the biological inoculant and it was found that the best results were given with the proportion of one part of inoculant in three parts of soil (w/w ratio). The differential expression of the glutathione-S-transferase GST gene was evaluated through real-time PCR and the concentration of heavy metals inside and outside the plant was evaluated with inductively coupled plasma atomic emission spectroscopy (ICP). It was found that the plants that were inoculated with mycorrhizae developed longer stems and shorter roots; in the same way, the GST gene had greater expression in the stem than in the root, largely because the roots help the filtration of nutrients to the stem, retaining metals and detoxifying by GST-catalyzed glutathione. Full article

Rare earth elements (REE) are known to be emerging contaminants in hydrosphere, but roles of hydrous manganese oxyhydroxides (HMO) in REE transport in groundwater remains unknown. In this study, groundwater was sampled along a flow path in the North China Plain to determine the behavior of REE surface complexation to HMO by a modeling and field study approach. Results show that the proportion of neodymium (Nd) complexed by HMO ranges from 0.2% to 95.8%, and from 0.3% to 99.6% in shallow groundwater and deep groundwater, respectively. The amount of complexed REE increases along the flow path. REE bound to HMO exhibit decreasing trends with increasing atomic number. The process was determined to be independent of pH, HMO content, and metal loading. This finding further demonstrates HMO-REE complexation plays a key role in transport of REE in groundwater through preferential scavenging of light REE (LREE) over heavy REE (HREE). Nevertheless, carbonate ligands appear to be robust competitors in reducing the amount of REE sorbed to HMO when solution pH rises above 8.0. Assuming that 50% of Mn concentration occurs as HMO, the amount of complexed REE was predicted to show a more marked decrease in LREE compared to that of HREE. Full article

In this study, models were used for the first time to investigate the fate and transport of rare earth elements (REE) in the presence of hydrous manganese and ferric oxides in groundwaters from the coastal Bohai Bay (China). Results showed that REE sorption is strongly dependent on pH, as well as hydrous manganese and ferric oxide content. Higher proportions of REE were sorbed by hydrous manganese oxide as compared to hydrous ferric oxides, for example in the presence of neodymium. In this case, a mean 28% of this element was sorbed by hydrous manganese oxide, whereas an average 7% sorption was observed with hydrous ferric oxides. A contrasting REE sorption behavior was observed with hydrous manganese and ferric oxide for all investigated groundwaters. Specifically, REE bound to hydrous manganese oxides showed decreasing sorption patterns with increasing atomic number. The opposite trend was observed in the presence of hydrous ferric oxides. In addition, these results suggested that light REE (from La to Sm) rather than heavy REE (from Eu to Lu) are preferentially scavenged by hydrous manganese oxide. However, the heavy REE showed a greater affinity for hydrous ferric oxides compared to light REE. Therefore, both hydrous manganese and ferric oxide are important scavengers of REE. This study shows the implication of hydrous manganese and ferric oxide sorption for the sink of REE in groundwater. Full article

Spatial concentrations and chemical fractions of heavy metals (Cr, Cu, Pb, Zn and Cd) in 16 sampling sites from the Honghu Lake were investigated using an atomic absorption spectrophotometer and optimized BCR (the European Community Bureau of Reference) three-stage extraction procedure. Compared with the corresponding probable effect levels (PELs), adverse biological effects of the studied five sediment metals decreased in the sequence of Cr > Cu > Zn > Pb > Cd. Geo-accumulation index (I_geo) values for Cr, Cu, Pb and Zn in each sampling site were at un-contamination level, while the values for Cd varied from un-contamination level to moderate contamination level. Spatially, the enrichment degree of Cd in lower part of the South Lake, the west part of the North Lake and the outlet were higher than the other parts of Honghu Lake. For metal chemical fractions, the proportions of the acid-extractable fraction of five metal contents were in the descending order: Cd, Cu, Zn, Pb and Cr. Cd had the highest bioaccessibility. Being the above indexes focused always on heavy metals’ total content or chemical fraction in deterministic assessment system, which may confuse decision makers, the fuzzy comprehensive risk assessment method was established based on PEI (Potential ecological risk index), RAC (Risk assessment code) and fuzzy theory. Average comprehensive risks of heavy metals in sediments revealed the following orders: Cd (considerable risk) > Cu (moderate risk) > Zn (low risk) > Pb > Cr. Thus, Cd and Cu were determined as the pollutants of most concern. The central part of South Honghu Lake (S4, S5, S6, S9, S12 and S14), east part of the North Honghu Lake (S1) and outlet of outlet of the Honghu Lake (S10) were recommended as the priority control areas. Specifically, it is necessary to pay more attention to S1, S4, S5, S6, S9 and S16 when decision making for their calculated membership values (probabilities) of adjacent risk levels quite close. Full article