Heavy Metal Cations Research Articles

Synthesis, crystal structure and exploration of N,N'-(ethane-1,2-diyl)bis(4-acetylbenzenesulfonamide) (EDBABS) fabricated glassy carbon electrode as highly sensitive barium (Ba2+) sensor: An electrochemical approach

Environmental pollution spurred by dint of noxious chemicals and heavy metals has popped up as a pressing threat for present day community. In this study, we synthesized the N,N'-(ethane 1,2-diyl)bis(4-acetylbenzene-1-sulfonamide) (EDBABS) and N,N'-(cyclohexane-1,2-diyl)bis(4-acetylbenzenesulfonamide) (CDBABS) as bidentate chelating agents with the intention to detect the heavy metal cations in water systems. Conventional spectroscopic techniques such as UV-Vis spectroscopy, Fourier transform-infra red (FT-IR) spectroscopy, 1H-NMR and 13C-NMR in addition to single crystal X-ray diffraction studies were performed to expound structural characterization data of these newly synthesized non-reported bidentate chelating agents. After Characterization, a novel electrochemical current – potential (I-V) approach based on their modified GCEs was applied to detect the toxic cations in water systems. For this purpose, Keithley electrometer was employed as a constant voltage source. On the trail of fabricating an efficient as well as selective electrochemical sensor, for the detection of heavy metal cations in phosphate buffer system of pH = 7.0, EDBABS and CDBABS coupled with nafion as adhesive conducting binder were coated separately onto the Glassy Carbon Electrodes (GCEs). it was delineated that newly designed EDBABS/Nafion/GCE induced a high current response for Ba2+ cations in the presence of other interfering heavy metal cations (Y3+, Sn2+, Sb3+, Mn2+, Hg2+, Cr3+, As3+ and Ag+) than CDBABS/Nafion/GCE and found to be selective and sensitive towards Ba2+ cations, predominantly contributing towards environmental pollution. In order to optimize this newly designed EDBABS/Nafion/GCE as selective electrochemical Ba2+ cationic sensor, different analytical parameters such as sensitivity, limit of detection (LOD) at S/N of 3, limit of quantification (LOQ), and linear dynamic range (LDR) turned out to be satisfactory towards Ba2+ cations. The calibration curve emerged to be linear with a broad concentration range of Ba2+ cations from 0.1 nM to 0.01M and sensitivity was estimated as 3.481 × 10−3µAµM−1cm−2 in addition to (r2) as 0.9834, limit of detection (LOD) as 0.027nM (at S/N=3) and limit of quantification (LOQ) as 0.091nM. Within the realm of extensive environmental protection and public health care field, this work inducts a reliable and effective way for the fabrication of sensitive as well as selective cationic electrochemical sensors based on chelating agents which can be launched as an advanced approach for quick probing of heavy metal cations in water systems, reliably and effectively.

Toward a realistic theoretical electronic spectra of metal aqua ions in solution: The case of Ce(H2O)n3+ using statistical methods and quantum chemistry calculations.

Accurately predicting spectra for heavy elements, often open-shell systems, is a significant challenge typically addressed using a single cluster approach with a fixed coordination number. Developing a realistic model that accounts for temperature effects, variable coordination numbers, and interprets experimental data is even more demanding due to the strong solute-solvent interactions present in solutions of heavy metal cations. This study addresses these challenges by combining multiple methodologies to accurately predict realistic spectra for highly charged metal cations in aqueous media, with a focus on the electronic absorption spectrum of Ce3+ in water. Utilizing highly correlated relativistic quantum mechanical (QM) wavefunctions and structures from molecular dynamics (MD) simulations, we show that the convolution of individual vertical transitions yields excellent agreement with experimental results without the introduction of empirical broadening. Good results are obtained for both the normalized spectrum and that of absolute intensity. The study incorporates a statistical machine learning algorithm, Gaussian Mixture Models-Nuclear Ensemble Approach (GMM-NEA), to convolute individual spectra. The microscopic distribution provided by MD simulations allows us to examine the contributions of the octa- and ennea-hydrate of Ce3+ in water to the final spectrum. In addition, the temperature dependence of the spectrum is theoretically captured by observing the changing population of these hydrate forms with temperature. We also explore an alternative method for obtaining statistically representative structures in a less demanding manner than MD simulations, derived from QM Wigner distributions. The combination of Wigner-sampling and GMM-NEA broadening shows promise for wide application in spectroscopic analysis and predictions, offering a computationally efficient alternative to traditional methods.

Hydrochar from sawdust and sewage sludge – a potential media for retaining heavy metals in sustainable drainage systems (SuDS)

ABSTRACT Waste valorization is an essential aspect of sustainable development. From this perspective, co-hydrothermal carbonization (Co-HTC) is a promising thermochemical process for converting organic waste into hydrochar. Hydrochar is a solid material whose physicochemical properties could make it suitable for adsorbing pollutants such as heavy metals. Accordingly, this work evaluated the hydrochar from Co-HTC of sawdust and non-dewatered sewage sludge as a potential adsorbent of heavy metals at low concentrations. In the context of sustainable drainage systems (SuDS), it is notable that heavy metals are present at very low but still potentially harmful concentrations, which presents a potential opportunity for the application of hydrochar. Thus, three hydrochars (H-180, H-215, and H-250), produced by Co-HTC at 180, 215, and 250 °C, were tested herein for their ability to retain lead (Pb2+). The H-180 presented better performance than other hydrochars (H-215 and H-250), suggesting that chemisorption could be the main adsorption mechanism. Interestingly, the presence of other cationic heavy metals (Cu2+, Zn2+, Cd2+, Cr6+, and Ni2+) did not hinder the Pb2+ adsorption, for which the removal efficiency remained close to 100%. In fact, in such a multi-metal system, hydrochar can be suitable for capturing both lead and cadmium. Therefore, the hydrochar from Co-HTC of sawdust and non-dewatered sewage sludge can be useful for removing heavy metals at low concentrations, such as those found in urban runoff waters. Although further studies are required, these findings suggest hydrochar as a potential material for application in SuDS.

Heterogeneous precipitation behavior and mechanism during the adsorption of cationic heavy metals by biochar: Roles of inorganic components

Heavy metals are commonly adsorbed by biochar in contaminated water and soil. However, the behaviour and underlying mechanisms of heterogeneous precipitation between the inorganic components of biochar and cationic heavy metals remain poorly understood. In this study, we comprehensively investigated the nucleation, growth, and aggregation of precipitates, ion exchange-coupled precipitation behaviour, adsorption-precipitation correlation, and the influence of environmental factors (e.g., anion content, pH, initial concentration, type of heavy metals, and biochar size). The kinetic results indicated that the generation of precipitates was accompanied by an adsorption reaction with a gradual increase in crystal size and aggregation behaviour. Moreover, precipitation includes both surface and solution precipitation. The increasing local concentration of Pb(II) around the biochar at high initial concentrations increased the supersaturation of the nucleating substance, which decreased the potential for heterogeneous nucleation and facilitated heterogeneous precipitation. Correlation analysis revealed the presence of a coupling mechanism between precipitation and cation exchange. The enhanced electrostatic attraction at high pH could lower the heterogeneous nucleation potential barrier, thus promoting heterogeneous precipitation. The small biochar size extended the induction time, which was unfavourable for heterogeneous nucleation. This study provides a deeper understanding of the heterogeneous precipitation behaviour of the inorganic components of biochar and cationic heavy metals.

Changes in physical and chemical properties of microplastics by ozonation

This study evaluated the altered properties of microplastics during the ozonation process in water matrices. The selected polymers include low-density polyethylene, high-density polyethylene, polypropylene, polystyrene, polyethylene terephthalate, and polyvinyl chloride. The morphology, contact angle, and chemical composition of the pristine and altered microplastics were characterized using field-emission scanning electron microscopy-energy dispersive spectrometry, contact angle analysis, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS). Microplastic oxidation can lead to surface abrasion, cracking, and fragmentation. XPS analysis indicated that a C=O double bond (carbonyl group) and carboxylic acid/ester bond (O−C=O) were generated in the ozone process. In addition, all the carbonyl index values increased, implying that the number of oxygen functional groups on the surface of the microplastics increased. The contact angle also decreased, indicating that the hydrophilic portion of the microplastics increased due to oxidation. Microplastics, whose surfaces are roughened owing to oxidation or reduced in size owing to fragmentation, pose a fatal threat to aquatic life. In addition, microplastics with increased oxygen functional groups and hydrophilicity due to oxidation treatment have different adsorption properties. Relatively hydrophilic microplastics adsorb heavy metal cations that can adversely affect ecosystems by acting as heavy metal transport mediators.

Resistance of cellular variants of Nicotiana tabaccum L. plants to water stress

Aim. It has been established that resistance to some heavy metal cations is combined with resistance to osmotic stress. Thus, resistance to barium cations correlates with resistance to water stress. Therefore, the aim of the experiment was to compare the resistance of primary and secondary calli to modelled stresses. Methods. The object of testing was tobacco, a plant sensitive to water deficit. The level of resistance of the variants was assessed by the relative increase in fresh weight under osmotic stresses: (salinity, 25.0 g/l of sea water salts; sodium sulphate, water stress). Both concentrations are lethal for wild-type tobacco cell cultures. Results. Вa-resistant tobacco cell cultures were obtained. Tobacco callus were resistant to lethal modelled stresses. The Ba-resistant culture was developed on medium with the addition of sea water salts and sodium sulphate. Conclusions. The phenomenon of resistance was selected as a result of primary selection on the medium with heavy metal ions. The level of osmotic resistance did not decrease with increasing cultivation time.

Bioinspired, Carbohydrate-Containing Polymers Efficiently and Reversibly Sequester Heavy Metals.

Water scarcity and heavy metal pollution are significant challenges in today's industrialized world. Conventional heavy metal remediation methods are often inefficient and energy-intensive, and produce chemical sludge. To address these issues, we developed a bioinspired, carbohydrate-containing polymer system for efficient and selective heavy metal removal. Using ring opening metathesis polymerization, we synthesized polymers bearing amphiphilic glucuronate side chains capable of selectively binding heavy metal cations in mixed media. In samples containing high concentrations of heavy metals (>550 ppb), these polymers rapidly form a filterable precipitate upon metal capture, reducing the concentration of cation to <1.5 ppb within 3 min, as measured by inductively coupled plasma mass spectrometry. This system effectively removes cadmium ions from highly contaminated solutions to levels below the Agency for Toxic Substances and Disease Registry limit for Cd2+ in drinking water and selectively removes both Cd2+ and Pb2+ from lake water spiked with trace amounts of metal. Acidification triggers protonation of the glucuronate groups, releasing the heavy metals and resolubilizing the polymer. This capture-and-release process can be repeated over multiple cycles without loss of binding capacity. As such, this study introduces a novel class of recyclable materials with pH-responsive properties, offering potential for applications in water remediation and beyond.

The superior adsorption capacity of biogenic α-Mn2O3 in comparison to chemogenic α-Mn2O3 for five divalent heavy metal cations and the adsorption mechanism of biogenic α-Mn2O3: Experimental and DFT investigations

Manganese oxides play a crucial role in the adsorption of heavy metals in the environment. However, there is currently a lack of information regarding the comparative adsorption efficiency of heavy metals between biogenic and chemogenic manganese oxides. In this work, we compared the adsorption performance of biogenic and chemogenic α-Mn2O3 towards Pb(II), Cd(II), Cu(II), Zn(II) and Ni(II). Mineral characterization analyses revealed that biogenic α-Mn2O3 exhibited a polycrystalline nature, whereas chemogenic α-Mn2O3 displayed a monocrystalline nature with a lower impurity content compared to biogenic α-Mn2O3. Under acidic conditions, biogenic α-Mn2O3 demonstrated a significantly higher adsorption capacity, ranging from 3 to 6 times greater than its chemogenic counterpart, within an initial heavy metal concentration range of 0.2–1.0 mM. This superiority can be attributed to the presence of more abundant functional groups and a greater content of hydroxyl O species on the surface of biogenic α-Mn2O3 in comparison to chemogenic α-Mn2O3. During the adsorption process of biogenic α-Mn2O3, there were observed ionic exchanges between Mn(II) and these cations. More importantly, biogenic α-Mn2O3 bound with these cations probably through the formation of -O/OH/S complexes. The adsorption selectivity of biogenic α-Mn2O3 towards the five heavy metals was experimentally determined to follow the order of Ni(II) > Pb(II) > Cu(II) > Zn(II) > Cd(II). The electronic interaction between biogenic α-Mn2O3 and these cations indicated that Ni(II), Pb(II) and Cu(II) were more likely to share electrons with O atoms on the surface of biogenic α-Mn2O3 compared to Zn(II) and Cd(II).

New fibrous carboxyl cation exchangers for sorption cations of heavy and non-ferrous metals from water

New fibrous carboxyl cation exchangers FIBAN were synthesized by the method of graft copolymerization to polypropylene staple fibers of acrylic acid and various bifunctional comonomers (divinylbenzene – DVB, ethyleneglycoldimethacrylate – EGDM, methylene-bis-acrylamide – MBAA). Sorption properties of the fibers towards cations of heavy and non-ferrous metals (Cо2+, Ni2+, Zn2+, Cd2+, Cu2+ и Pb2+) were studied on the model solutions in the dynamic regime. The dynamic activity of the crosslinked sorbents towards Cu2+ and Pb2+ ions is higher compared to fibrous analogues FIBAN Х-1, FIBAN Х-2, FIBAN К-6М, FIBAN К-5, VION КN-1. The best sorbent for lead ions between the crosslinked fibers is the fiber with EGDM. The fiber with MBAA has a higher affinity towards the cations of Ni2+, Zn2+, Cd2+ and Cа2+, which increases with the increasing of the degree of crosslinking by MBAA. Studying the fibers by the methods of Fourier-transform IR-spectroscopy, scanning electron microscopy, analyzing of the chemical oxygen demand in water extracts and determination of the equivalent moisture capacity coefficient coefficient demonstrated that the crosslinking by MBAA provides a stable structure of the sorbent. The high stability of the crosslinked structure combined with the high ion exchange capacity near 7 mEq/g and dynamic activity towards the cations of Pb2+, Zn2+, Cd2+ и Cа2+ makes the fibrous carboxyl sorbent with MBAA safe and perspective for drinking water purification.

Control for selective sorption of heavy metals cations with anion exchanger AB-17-8 by modifying the surface with citrate groups

The citric acid modification produces an intermediate layer on the AB-17-8:C6H8O7 surface; the layer, on one hand, is firmly secured to the surface owing to the electrostatic coupling between the citrate anion and the positively charged trimethylammonium centers of the anion exchanger surface; on the other hand, it has carbonyl groups with a local negative electron density. The sorption of heavy metals cations occurs through coordination interactions via electrostatic mechanism with local centers of negative electron density, in particular, with the carbonylic oxygen atom.

Remediation of Arsenic and Heavy Metals and Soil Stabilization by Waste Chitosan based Biochar

Objectives : This study aims to evaluate the feasibility of converting waste chitosan adsorbents, laden with microalgae, into biochar for application as a stabilizing agent to remediate heavy metal-contaminated soil and improve soil quality.Methods : Waste chitosan adsorbents were converted into biochar through two processes: dry thermal carbonization at 400°C to produce pyrochar and hydrothermal carbonization at 200°C to produce hydrochar. The elemental compositions, surface functional groups, morphologies of the biochars were evaluated by elemental analyzer, FT-IR spectrometer, and SEM analysis. The arsenic and heavy metal adsorption characteristics of the produced biochars were assessed. Additionally, the produced biochars were applied as stabilizing agents to arsenic and heavy metal-contaminated soil with varying mixing ratios of 2, 5 and 10 wt%. After a one-week soil stabilization experiment, soil properties and TCLP(Toxicity Characteristic Leaching Procedure) leaching tests were conducted.Results and Discussion : The pyrochar produced from waste chitosan exhibited a porous structure with high pH (pH 10) and minimal surface functional groups. The hydrochar consisted of spherical particles with functional groups such as hydroxyl and amine groups on the surface, exhibiting a slightly acidic pH of 5.8. Pyrochar has a higher adsorption capacity for cationic heavy metals compared to hydrochar due to its porous structure and high pH. On the other hand, when applied to soil, hydrochar demonstrated superior stabilization efficiency for arsenic and heavy metals. This is attributed to the diverse surface functional groups containing oxygen on the hydrochar. The stabilization efficiency was influenced by the biochar mixing ratio, with a 5% hydrochar application resulting in 10-64% stabilization efficiency for all elements.Conclusion : This study confirmed that biochar produced from waste chitosan effectively stabilizes arsenic and heavy metals in soils. Additionally, the quantity of biochar used can impact its effectiveness in stabilization.

Novel Triton X-114 coated Fe3O4 magnetic nanoparticle adsorbent for Cd(II) and Co(II) ions preconcentration in honey samples using magnetic solid-phase extraction: Determination by ICP-OES

This work focuses on creating and studying the effectiveness of Fe3O4 nanoparticles coated with (3-aminopropyl)triethoxysilane (APTES) and polyethylene glycol tert-octylphenyl ether (TX-114), respectively, as adsorbent. Fe3O4@APTES@TX-114 adsorbent extracts heavy metal cations Cd2+ and Co2+ using a magnetic solid phase extraction technique. The synthesized magnetic nanoparticles (MNPs) were characterized by Field Emission Scanning Electron Microscope (FESEM), Energy Dispersive X-Ray Analysis (EDX), Fourier Transform Infrared Spectroscopy (FT-IR), and Thermogravimetric Analysis (TGA). After this stage, Cd2+ and Co2+ determinations were made with the ICP-OES device. The optimum conditions for recovering Cd2+ and Co2+ cations were pH 7, an adsorbent dosage of 2 g/L, and a contact time of 120 min. While the method was compatible with Langmuir and Freundlich isotherm models, the pseudo-second-order kinetic equation was more compatible than the pseudo-first-order. Acidic and basic media were investigated for the desorption of Cd2+ and Co2+ ions from the adsorbent. At the same time, maximum recovery was achieved for both cations at a concentration of 1.5 mol/L HCl, but no significant recovery was obtained in the NaOH medium. The common ion study observed that Cd2+ and Co2+ cations were recovered over 95 % in the presence of many cations and anions at different concentrations. The relative standard deviation (RSD), limit of quantification (LOQ), limit of detection (LOD), and enrichment factor (EF) were calculated as 1.40 %, 2.963 µg/L, 0.889 µg/L, 20.99 for Cd2+ and 3.05 %, 1.88 µg/L, 0.564 µg/L, 109.41 for Co2+, respectively. The magnetic solid phase extraction method realized quantitative recovery of Cd2+ and Co2+ cations in different honey samples. It was found that the heavy metal contents in honey samples from the Sakarya region are below permissible levels.

Mechanism and application of bacterial exopolysaccharides: An advanced approach for sustainable heavy metal abolition from soil

The escalation of heavy metal pollutants in soils and effluents, driven by industrialization and human activities, poses significant environmental and health risks. Conventional remediation methods are often costly and ineffective, prompting a shift towards sustainable alternatives such as biological treatments. Natural biosorbents, including microbial cells and their byproducts, have emerged as promising solutions. One such approach involves leveraging exopolysaccharides (EPS), complex high-molecular-weight biopolymers synthesized by microbes under environmental stress conditions. EPS are intricate organic macromolecules comprising proteins, polysaccharides, uronic acids, humic compounds, and lipids, either located within microbial cells or secreted into their surroundings. Their anionic functional groups enable efficient electrostatic binding of cationic heavy metals, making EPS effective biosorbents for soil remediation. This review thoroughly explores the pivotal role of bacterial EPS in the removal of heavy metals, focusing on EPS biosynthesis mechanisms, the dynamics of interaction with heavy metals, and case studies that illustrate their effectiveness in practical remediation strategies. By highlighting these aspects, the review underscores the innovation and practical implications of EPS-based bioremediation technologies, demonstrating their potential to address critical environmental challenges effectively while paving the way for sustainable environmental management practices. Key findings reveal that EPS exhibit robust metal-binding capacities, facilitated by their anionic functional groups, thereby offering a promising solution for mitigating metal pollution in diverse environmental matrices.

Near-infrared fluorescent probe visual detection of Hg2+ and its application in biological system and ecological system

Mercury ion (Hg2+), a heavy metal cation with greater toxicity, is widely present in the ecological environment and has become a serious threat to human health and environmental safety. Currently, developing a solution to simultaneously visualize and monitor Hg2+ in environmental samples, including water, soil, and plants, remains a great challenge. In this work, we created and synthesized a near-infrared fluorescent probe, BBN-Hg, and utilized Hg2+ to trigger the partial cleavage of the carbon sulfate ester in BBN-Hg as a sensing mechanism, and the fluorescence intensity of BBN-Hg was significantly enhanced at 650 nm, thus realizing the visualization of Hg2+ with good selectivity (detection limit, 53 nM). In live cells and zebrafish, the probe BBN-Hg enhances the red fluorescence signal in the presence of Hg2+, and successfully performs 3D imaging on zebrafish, making it a powerful tool for detecting Hg2+ in living systems. More importantly, with BBN-Hg, we are able to detect Hg2+ in actual water samples, soil and plant seedling roots. Furthermore, the probe was prepared as a test strip for on-site determination of Hg2+ with the assistance of a smartphone. Therefore, this study offers an easy-to-use and useful method for tracking Hg2+ levels in living organisms and their surroundings.

Development of pivalic acid conjugated Nafion modified glassy carbon electrode for sensitive detection of Cu(II) by electrochemical approach

In this work, pivalic acid (pivH) molecule is employed for an electrochemical sensing of copper cations in an aqueous medium. For sensitive as well as selective potential sensor application, pivH was fabricated onto a glassy carbon electrode (GCE) facilitated by adhesive conducting binder, nafion, so as make it selective and effective electrochemical probe (pivH/Nafion/GCE) towards specific heavy metal cations. This newly fabricated pivH/Nafion/GCE reveals enhance electrochemical activity toward copper ions in the presence of other interfering heavy metal cations in phosphate buffer solution (PBS) of pH=7. The calibration plot was linear (r2 = 0.9879) across broad linear dynamic range (LDR) spanning Cu2+ concentration from 0.1 nM to 0.01 M. The sensitivity and detection limit was found to be 0.0212 × 10−2 µAµM−1cm−2 and 0.014 nM, respectively. So, this newly fabricated GCE as selective electrochemical probe offers a sensitive as well as selective detection of Cu2+ cations in real environmental samples using a novel electrochemical, current–potential (I-V), approach, for the first time. Further, we explored pivalic acid for the preparation of new di-nuclear copper complex, [Cu2(piv)4(pivH)2] (where piv = pivalate; pivH=pivalic acid) and characterized by Fourier transform infrared spectroscopy (FTIR) spectroscopy, elemental analysis and single crystal X-ray diffractometry. Density functional theory (DFT) calculations were carried out to confirm the interactions and these calculations well-support to experimental data. In case of deprotonated form of pivH, Molecular Electrostatic Potential (MEP) analysis exhibits electrostatic potential equals to −148.4 kcal/mol which suggest about the strong interaction of –COOH with copper centers. Similarly, interaction energies, the quantum theory of atoms in molecules (QTAIM) study and Natural Bond Orbital (NBO) analysis also favor to experimental work. Thus, this novel study demonstrates an excellent approach for highly selective and sensitive detection of Cu2+ cations in short response time with low detection limit and good reproducibility by using I-V method based on newly designed pivH/Nafion/GCE as selective Cu2+ cationic electrochemical sensor. The experimental data was compactable with theoretical calculations.

Sulfidation−reoxidation enhances heavy metal immobilization by vivianite

Iron minerals in nature are pivotal hosts for heavy metals, significantly influencing their geochemical cycling and eventual fate. It is generally accepted that, vivianite, a prevalent iron phosphate mineral in aquatic and terrestrial environments, exhibits a limited capacity for adsorbing cationic heavy metals. However, our study unveils a remarkable phenomenon that the synergistic interaction between sulfide (S2−) and vivianite triggers an unexpected sulfidation−reoxidation process, enhancing the immobilization of heavy metals such as cadmium (Cd), copper (Cu), and zinc (Zn). For instance, the combination of vivianite and S2− boosted the removal of Cd2+ from the aqueous phase under anaerobic conditions, and ensured the retention of Cd stabilized in the solid phase when shifted to aerobic conditions. It is intriguing to note that no discrete FeS formation was detected in the sulfidation phase, and the primary crystal structure of vivianite largely retained its integrity throughout the whole process. Detailed molecular-level investigations indicate that sulfidation predominantly targets the Fe(II) sites at the corners of the PO4 tetrahedron in vivianite. With the transition to aerobic conditions, the exothermic oxidation of CdS and the S sites in vivianite initiates, rendering it thermodynamically favorable for Cd to form multidentate coordination structures, predominantly through the Cd-O-P and Cd-O-Fe bonds. This mechanism elucidates how Cd is incorporated into the vivianite structure, highlighting a novel pathway for heavy metal immobilization via the sulfidation−reoxidation dynamics in iron phosphate minerals.

Understanding Zinc Transport in Estuarine Environments: Insights from Sediment Composition

Sediments are sources and sinks of heavy metals in water, and estuaries are heavily influenced by human production and life. Therefore, it is of great significance to study the composition of estuarine sediments and the relationship between their components to understand the transport and transformation pathways of heavy metals in the environment. In this research, we investigated the characteristics and patterns of Zn adsorption by organic–inorganic composites, organic–clay mineral composites, and iron oxide–clay mineral composites in eight estuarine sediment samples from Dianchi Lake. The results show that both Langmuir and Freundlich isothermal models can describe the adsorption behaviour of the adsorbent better. The order of the adsorption capacity of the three groups of samples for zinc was organic–inorganic composites &gt; organic–clay mineral composites &gt; iron oxide–clay mineral composites. Through FTIR and XRD analyses, the adsorption of Zn2+ on the three groups of samples was dominated by electrostatic attraction and coordination adsorption, accompanied by the occurrence of ion exchange and co-precipitation. After FTIR semi-quantitative analysis, it was found that the source of the differences in the high and low Zn adsorption of the three types of samples may be mainly due to the content of phenolic functional groups in the organic matter. This may be related to the low redox site of the phenolic hydroxyl group, which, as an electron donor, is susceptible to electrostatic attraction and complexation with heavy metal cations. The organic–inorganic composite has a higher adsorption capacity for Zn when the ratio of the active fraction of organic matter to the free iron oxide content is 0.65–0.70. In this range, the organic matter can provide enough negative charge without making the sample surface too dense. Iron oxides can also activate the sample by providing sufficient contact between the clay minerals and the organic matter. When this ratio is too high or too low, it will be unfavourable for Zn adsorption.

Effective Removal of Pb(II) from Multiple Cationic Heavy Metals—An Inexpensive Lignin-Modified Attapulgite

To develop cost-effective heavy metal adsorbents, we employed water-soluble lignin from black liquor to modify activated attapulgite, resulting in the creation of a novel adsorbent called Lignin-modified attapulgite (LATP). In this study, scanning electron microscopy and Fourier transform infrared spectrometer techniques were utilized to characterize the structural details of LATP. The results revealed that lignin occupies the micropores of attapulgite, while additional functional groups are present on the attapulgite surface. We conducted adsorption tests using LATP to remove five types of heavy metal ions (Cd2+, Pb2+, Zn2+, Mn2+, Cu2+), and it was found that LATP exhibited greater removal mass and binding strength for Pb(II) compared to the other ions. For further investigation, batch experiments were performed to evaluate the adsorptive kinetics, isotherms, and thermodynamics of Pb2+ removal from aqueous solutions using LATP. The results indicated that the adsorption capacity of Pb(II) on LATP decreased with decreasing pH, while the presence of Na+ had no effect on adsorption. The adsorption process reached equilibrium rapidly, and the Langmuir adsorption capacities increased with temperature, measuring 286.40 mg/g, 315.51 mg/g, and 349.70 mg/g at 298 K, 308 K, and 318 K, respectively. Thermodynamic analysis revealed positive values for ΔH0 and ΔS0, indicating an endothermic and spontaneous adsorption process. Furthermore, ΔG0 exhibited negative values, confirming the spontaneous nature of the adsorption. Consequently, LATP demonstrates great potential as an effective adsorbent for the removal of Pb(II). Therefore, LATP shows great potential as an effective adsorbent for the removal of Pb(II) from natural water environments, contributing to the sustainable development of man and nature.

Acetate anions intercalated Fe/Mg-layered double hydroxides modified biochar for efficient adsorption of anionic and cationic heavy metal ions from polluted water

The simultaneous removal of anionic and cationic heavy metals presents a challenge for adsorbents. In this study, acetate (Ac-) was utilized as the intercalating anion for layered double hydroxide (LDH) to prepare a novel biochar composite adsorbent (Ac-LB) designed for the adsorption of Pb(II), Cu(II), and As(V). By utilizing Ac- as the intercalating anion, the interlayer space of the LDH was enlarged from 0.803 nm to 0.869 nm, exposing more adsorption sites for the LDH and enhancing the affinity for heavy metals. The results of the adsorption experiments showed that the adsorption effect of Ac-LB on heavy metals was significantly improved compared to the original FeMg-LDH modified biochar composites (LB), and the maximum adsorption capacity of Pb(II), Cu(II), and As(V) were 402.70, 68.50, and 21.68 mg/g, respectively. Wastewater simulation tests further confirmed the promising application of Ac-LB for heavy metal adsorption. The analysis of the adsorption mechanism revealed that surface complexation, electrostatic adsorption, and chemical deposition were the main mechanisms of action between heavy metals (Pb(II) and Cu(II)) and Ac-LB. Additionally, Cu(II) ions underwent a homogeneous substitution reaction with Ac-LB. The adsorption process of As(V) by Ac-LB mainly relied on complexation and ion-exchange reactions. Lastly, the modification of the LDH structure by Ac− as an intercalating anion, thereby increasing the affinity for heavy metals, was further illustrated using density-functional theory (DFT) calculations.

Multistage stabilization of Cd, Pb, Zn, Cu and As in contaminated soil by phosphorus-coated nZVI layered composite materials: characteristics, process and mechanism

This study developed a shell-like slow-release material, PF@ST/Fe-0.5, by encapsulating nanoscale zero-valent iron composites (NZC) with phosphate fertilizer (PF) and a starch binder (ST). The material dissolved in soil in stages, first releasing P and Ca to increase the soil pH from 4.95 to 7.14. This was followed by the formation of phosphates and hydroxides precipitates with Pb, Cu, Zn, and Cd in soil, reducing their bioavailable forms by 81.73 %, 79.58 %, 91.05 %, and 86.47 %, respectively. The process also involved the competitive adsorption between PO43-/HPO42- and arsenate/arsenite led to the release of specifically adsorbed arsenic, increasing the probability of reaction with the material. Afterwards, the exposure of the NZC core reacted with arsenate/arsenite to form ferric arsenates, thus reducing the content of bioavailable arsenic in the soil by 73.57 %. Excess PO43- and alkali metal cations were captured and mineralized by the iron (hydro) oxides and reactive silicates in NZC, enhancing the remediation effect. Furthermore, the wet-dry alternation test had demonstrated the adaptability of PF@ST/Fe-0.5 to the rainy dry-wet soil environment in Yunnan, which enabled the bioavailable content of As, Pb, Cu, Zn, and Cd decreased by 71.2 %, 94.8 %, 84.1 %, 79.8 %, and 83.9 %, respectively. The layered structure minimized internal reactive substance consumption and protected the internal nZVI from oxidation. The phased release of phosphate and Fe0 stabilized Pb, Cu, Zn, and Cd, enhancing As stabilization and providing a new perspective for the synchronous stabilization of soil contaminated.