Search Results (67)

Greenhouse environments with restricted air exchange favor the accumulation of gaseous elemental mercury (GEM), posing potential exposure risks. However, the exact contribution of soil–air mercury fluxes to ambient greenhouse GEM, and the mechanisms by which organic manure application regulates this process, represent a critical knowledge gap. To address this, a 90-day simulated greenhouse incubation experiment (incorporating 0%, 1%, 2%, and 3% sheep manure fertilizer (SMF) amendments) and continuous 24 h micro-meteorological monitoring were conducted to evaluate GEM dynamics, soil Hg(0) fluxes, and mercury valence-state partitioning. Furthermore, macroscopic Hg(II) adsorption–desorption experiments were performed to elucidate the retention mechanisms. Our results demonstrated that while mechanical fertilization disturbances caused a transient short-term release of pre-existing Hg(0) on Day 0, both ambient GEM concentrations and soil Hg(0) emission fluxes generally declined over the long-term incubation period. Soil Hg(0) emission was identified as the predominant source process driving greenhouse GEM dynamics. Crucially, SMF addition consistently decreased operationally defined soil Hg(0) while relatively increasing the oxidized Hg(I) and Hg(II) fractions. Macroscopic batch experiments corroborated that SMF significantly enhanced Hg(II) retention and reduced its reactivation potential. Overall, under controlled experimental conditions, SMF exhibited a strong time-dependent suppressive effect on soil Hg(0) release and ambient GEM accumulation. These findings highlight the potential of organic manure in mitigating mercury risks in protected agriculture, though future molecular-level spectroscopic validations remain necessary to deduce the precise binding mechanisms. Full article

Mercury contamination in water poses severe environmental and health risks, requiring efficient and sustainable removal strategies. In this study, rice husk (RH), rice husk-derived materials, including rice ash (RHA), and Mobil Composition of Matter No. 41 (MCM-41) were evaluated as adsorbents for Hg(II) removal in aqueous systems. Among the tested materials, MCM-41 exhibited superior adsorption performance, achieving up to 98% Hg(II) removal under optimal conditions (pH 6.8, 3 g L⁻¹ of adsorbent, and a pollutant concentration of 0.90 mg L⁻¹). Adsorption followed a pseudo-second-order kinetic model and was best described by the Langmuir isotherm, indicating monolayer adsorption. The maximum adsorption capacity reached 0.80 mg g⁻¹. Thermodynamic analysis revealed that the process was spontaneous and exothermic, primarily governed by coordination interactions and hydrogen bonding with surface silanol groups. The adsorbent’s applicability was further assessed in distilled water, synthetic industrial wastewater, and river water. Although high removal efficiencies were maintained, a decrease was observed in complex matrices due to competition from coexisting ions. Reusability tests demonstrated that MCM-41 retained its performance over four adsorption cycles. Environmental safety was evaluated through ecotoxicological and microbiological assays. Daphnia magna exhibited high sensitivity to Hg(II) (EC₅₀ values of 0.0220 mg L⁻¹ at 24 h and 0.0158 mg L⁻¹ at 48 h), while treated samples showed improved germination indices of Lactuca sativa, particularly in distilled and river water. However, residual toxicity persisted in industrial wastewater matrices. Overall, rice husk-derived MCM-41 is a promising and sustainable adsorbent for Hg(II) removal, though further optimization is needed to mitigate residual toxicity in complex water matrices. Full article

Mercury pollution from artisanal and small-scale gold mining remains one of the most persistent environmental threats due to the high toxicity, mobility, and bioaccumulation of Hg(II). In this work, Colombian banana pseudostem waste is valorized into a lignocellulosic carbocatalyst through pyrolysis at 500 °C followed by MnCO₃-derived MnOx functionalization, producing a sustainable material for Hg(II) remediation. The transformation of the biomass leads from a fibrous structure (~25 µm) to a pyrolyzed carbon matrix (9.56 µm), and finally to a heterogeneous Mn-modified system with bimodal particle distribution (~25 µm and ~0.85 µm), the latter being associated with highly dispersed MnOx redox-active domains. Structural and textural analyses reveal that Mn incorporation significantly enhances surface properties, increasing the BET surface area from 140.8 to 213 m² g⁻¹ while reducing pore size to the meso–microporous range (~1.9 nm). Importantly, the material retains intrinsic minerals such as Ca, Mg, K, and Si, which contribute to surface basicity and ion-exchange capacity, supporting additional Hg(II) interaction pathways. Optical and electronic characterization shows a wide band gap semiconductor behavior (≈3.4 eV) and a conduction band position at −0.892 V vs. NHE, sufficiently negative to thermodynamically drive Hg²⁺ reduction to Hg⁰ under UV-A irradiation. Hg(II) quantification was validated using a UV–Vis method based on the Hg²⁺–dipicolinic acid (DPA) complex, confirming stable complex formation with 1:2 stoichiometry (Hg²⁺:DPA) and high analytical reliability (R² = 0.948, LOD = 1.85 mg L⁻¹). Photocatalytic experiments demonstrated negligible Hg(II) reduction under UV-A light in the absence of catalyst, whereas the carbon-based materials enabled significant Hg transformation through adsorption-assisted photoinduced electron transfer. Electrochemical analyses (Rct ≈ 11 Ω) confirmed efficient charge transport, while cyclic voltammetry evidenced reversible Mn(IV)/Mn(III)/Mn(II) redox cycling, which sustains electron mediation during photocatalysis. Overall, pristine biochar acts primarily through adsorption driven by oxygenated functional groups and porous structure, whereas Mn-functionalized biochar operates via a synergistic adsorption–photocatalytic mechanism. In this system, MnOx species function as redox-active centers that facilitate electron transfer from the carbon matrix to Hg(II), while the conductive lignocellulosic-derived framework enhances charge mobility. The combination of structural carbon stability, dispersed Mn active sites, and inherent mineral functionality establishes a highly efficient and sustainable carbocatalyst, demonstrating a green and scalable approach for mercury remediation in mining-impacted regions. Full article

A previously unexplored magnetic biocomposite (CMC-HSDs/Fe₃O₄) was developed through the valorization of hydrophobic scleroprotein discards (HSDs). The synthesized material was evaluated for its efficacy in the adsorption of Cr(VI) and Hg(II) ions from contaminated aqueous systems. The physicochemical properties of the synthesized CMC-HSDs/Fe₃O₄ nanocomposite were characterized using XRD, FTIR, BET, TG/DTG, FESEM, EDX, and elemental mapping. Subsequently, a Box–Behnken experimental design was employed to model and optimize the adsorption process for Cr(VI) and Hg(II), focusing on the critical parameters of solution pH, adsorbent dosage, and interaction time. Kinetic data were best fitted to the pseudo-first-order (PFO) model. Equilibrium isotherm analysis revealed that Cr(VI) adsorption followed the Langmuir model, while Hg(II) adsorption was better fitted by the Freundlich model. Advanced ionic calculations elucidated a consistent multimolecular adsorption mechanism for both ions, characterized by temperature invariance and a preferential vertical geometry of the adsorbed species. Through a production cost of 25.56 USD/kg, the biosorbent demonstrates excellent reusability, retaining 88.60% efficiency for Cr(VI) and 85.69% for Hg(II) after five adsorption–desorption cycles. Based on a 50 mg/L influent concentration, projected treatment costs are ~$3.50/100 L for Cr(VI) and ~$1.22/100 L for Hg(II), underscoring the nanocomposite’s economic feasibility for industrial deployment in advanced tertiary wastewater remediation. Full article

A metal-free multicomponent polymerization (MCP) method was developed for synthesizing sulfur-containing polythioamides, using elemental sulfur, dicarboxylic acids, and diamines as monomers. This approach offers a versatile strategy for producing polythioamides with excellent thermal stability and high mechanical strength. The synthesized polymers demonstrated a maximum Hg(II) adsorption capacity of 187 mg·g⁻¹, with adsorption efficiencies exceeding 90% for most polymers. Both aliphatic and aromatic polythioamides showed similar high adsorption performance, indicating the universal applicability of this synthesis method. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) confirmed the strong interaction between Hg(II) ions and the sulfur-containing thioamide groups. These results highlight the potential of MCP-based polythioamides as efficient adsorbents for mercury removal, with promising applications in environmental remediation. Full article

Mercury (Hg) contamination in water and soil poses severe ecological and human health risks, yet conventional sorbents often suffer from limited capacity, selectivity, and stability. Here, we report a bifunctional porous organic polymer (AMTD-TCT) rationally constructed by covalently crosslinking 2-amino-5-mercapto-1,3,4-thiadiazole with trichlorotriazine, thereby integrating abundant sulfur and nitrogen coordination sites within a stable mesoporous framework. AMTD-TCT exhibits an ultrahigh Hg(II) adsorption capacity of 1257.7 mg g⁻¹, far exceeding most reported porous sorbents. Adsorption follows monolayer chemisorption, governed by strong S–Hg and N–Hg coordination and Na⁺/Hg²⁺ ion exchange, while hierarchical porosity ensures rapid diffusion and efficient utilization of active sites. The polymer maintains robust performance over a wide pH range and demonstrates strong retention with minimal desorption, underscoring its environmental durability. These findings highlight AMTD-TCT as a highly effective and scalable platform for Hg(II) remediation in complex aqueous–soil systems and illustrate a generalizable molecular design strategy for developing multifunctional porous polymers in advanced separation and purification technologies. Full article

In this study, kaolinite-based clay (Ka-Clay) was used as an adsorbent for the efficient removal of Pb(II), Cd(II) and Hg(II) ions from aqueous media. The selection of Pb(II), Cd(II) and Hg(II) ions for experimental studies took into account their high toxicity, while the choice of Ka-Clay, the ease of preparation and high availability of this material were the most important arguments. Ka-Clay exhibits high adsorption performance, with removal percents over 98% for Pb(II) and 93% for Cd(II), even at high concentrations of metal ions (over 150 mg/L, pH = 6.5, 4 g adsorbent/L, 21 ± 1 °C). For Hg(II) ions, the adsorption percent does not exceed 55%, and this moderate value is mainly due to the significant change in pH. The adsorption behavior was in accordance with the Langmuir model (R² > 0.95) and the pseudo-second order kinetic model (R² > 0.99), indicating an adsorption process that occurs mainly through chemical interactions at the adsorbent surface between the metal ions and the functional groups. Adsorption processes are spontaneous (ΔG = −8.66 ÷ −15.76 kJ/mol) and endothermic (ΔH = 7.09 ÷ 21.81 kJ/mol), and the adsorption mechanism is the results of elementary processes of electrostatic attraction, ion exchange and superficial complexation. The insignificant effect of other ions (Ca(II), Mg(II), Na(I), K(I)) present in real wastewater samples as well as the desorption behavior of exhausted adsorbent highlight the practical utility of this adsorbent on a large scale. The experimental results included in this study suggest that Ka-Clay can be used as a promising adsorbent for the removal of high concentrations of toxic heavy metals with low cost and high efficiency, and this can contribute to the design of a sustainable wastewater treatment method. Full article

Zero-valent iron (ZVI), particularly in its nanoscale form (nZVI), is now considered a highly promising material for the remediation of toxic metal ions from polluted groundwater owing to its strong reductive potential, significant surface area, and reactive behavior. This review systematically explores the application of pristine and modified ZVI systems—including doped ZVI, bio-stabilized composites, and ZVI supported on advanced materials like MXene and nanocellulose—for effective treatment of water containing metal species like As(III/V), Hg(II), Cr(VI), and Ni(II). Emphasis is placed on understanding the underlying mechanisms, including redox reactions, surface complexation, and synergistic adsorption–reduction pathways. Key factors affecting adsorption efficiency—such as pH, temperature, ZVI dosage, and competing ions—are thoroughly analyzed, alongside adsorption kinetics and isotherm models. Modified ZVI composites exhibit enhanced stability, selectivity, and reusability, demonstrating promising performance even in complex aqueous environments. Despite significant progress, challenges such as nanoparticle passivation, limited field-scale data, and potential toxicity of byproducts remain. The review concludes by highlighting future research directions focused on improving material longevity, regeneration efficiency, selective adsorption, and integration with other advanced remediation technologies for sustainable and scalable groundwater treatment. Full article

Chitosan (CS) and polyvinyl alcohol (PVA) nanofiber membranes were synthesized via electrospinning and used as supporting materials for powdered porous organic polymer (POP). These membranes were then crosslinked with glutaraldehyde, resulting in nanofiber membranes (CS/PVA/POP) as an efficient adsorbent for Hg(II) ions. Characterization using Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy showed that the membranes effectively removed up to 92.9% of mercury ions at optimal conditions, with an adsorption capacity of 116.1 mg/g. The adsorption data fit well with the Langmuir isotherm and pseudo-second-order kinetic models. The efficient uptake of mercury ions was attributed to chemisorption involving active groups (C=S, -NH₂, -OH), facilitated by mechanisms such as chelation, complexation, or electron exchange. The CS/PVA/POP nanofiber membranes demonstrated significant advantages in adsorption capacity, economic viability, and recyclability, providing an effective solution to mercury pollution in water. Full article

Nano-fibrillated bacterial cellulose (NFBC) has very long fibers (>17 μm) with diameters of approximately 20 nm. Hence, they have a very high aspect ratio and surface area. The high specific surface area of NFBC can potentially be utilized as an adsorbent. However, NFBC has no functional groups that can bind metal ions, limiting its potential applications. In this study, the hydroxyl groups on the surface of NFBC were chemically modified with EDTA monoanhydride to convert NFBC into a metal adsorbent. The fiber morphology and crystal structures of the modified NFBC were almost identical to those of the unmodified NFBC, suggesting that the surface hydroxyl groups of NFBC were well-conjugated with the EDTA groups. Surface-modified NFBC preferentially adsorbed transition metals in aqueous solutions, such as Cu(II), Hg(II), Pb(II), and Cd(II), but hardly adsorbed Mg(II) and Cr(VI). The adsorption of heavy metal ions can be explained by the pseudo-second-order kinetics of the chemisorption process and the Langmuir isotherm model. Furthermore, the EDTA-modified NFBC is a renewable and recyclable adsorbent. The results of this study indicate that surface-modified NFBC can be utilized as a biosorbent for heavy metal removal in chemical, food, pharmaceutical, and other industrial fields. Full article

This article reports the preparation of a novel functionalized magnetic nanoadsorbent through an addition reaction between Fe₃O₄ nanoparticles coated with allyl silica gel and 4-pyridinyl ethylene. A detailed characterization of Fe₃O₄@SiO₂-yl-VP was conducted. Among them, in the infrared spectrum, we can easily see that the absorption peak of the C=C stretching vibration at 1660 cm⁻¹ in the raw material disappears after the addition reaction, indicating the successful grafting of polymer on the surface of silica gel. The appearance of N element in the EDS spectrum also proves the successful completion of the addition reaction and the successful synthesis of Fe₃O₄@SiO₂-yl-VP. At pH = 5 and pH = 7, it only takes half an hour for Fe₃O₄@SiO₂-yl-VP to achieve maximum adsorption capacities of 85.06 and 73.78 mg/g for Hg (II) and Pb (II), respectively. The adsorption process conforms to the Langmuir model and the pseudo-first- and pseudo-second-order kinetic models and can be reused 11 times, demonstrating excellent reusability. Full article

Adsorption is one of the most promising strategies for heavy metal removal. For Hg(II) removal, mineralized Ca-based shell-type self-assembly beads (MCABs) using alginate as organic polymer template were synthesized in this work. The adsorbent preparation consists of gelation of a Ca-based spherical polymer template (CAB) and rate-controlled self-assembly mineralization in bicarbonate solution with various concentrations. The comparative study demonstrates that 1% (MCAB-1) is the optimal concentration of bicarbonate. Based on this condition, the maximum adsorption capacity (48 ± 4 mg/g) of MCAB-1 was observed at pH = 5 in a batch test, which was 2.67 times more than that of the unmodified one, CAB, at 18 ± 1 mg/g. Long-duration (10 h) adsorption tests showed that MCAB-1 exhibited remarkable performance stability and anti-wear ability (43.2% removal efficiency and 74.3% mass retention, compared to 2.7% and 38.6% for CAB at pH = 3, respectively). The morphology determination showed that a shell-type porous amorphous carbonate layer was formed at the surface of the organic polymer template by rate-controlled self-assembly mineralization. This transition not only promotes the pore structure and activated cation binding functional sites, but also improves the anti-wear ability of materials effectively. Full article

Functionalized nanomaterials with surface-active groups have garnered significant research interest due to their wide-ranging applications, particularly in water treatment for removing various contaminants. This study focuses on developing a novel, multi-functional nanobiosorbent by synthesizing nanosized biochar from artichoke leaves (NBAL) and molybdic acid (MA). The resulting nanobiosorbent, MA@NBAL, is produced through a microwave-irradiation process, offering a promising material for enhanced environmental remediation. The characteristics of assembled MA@NBAL were evaluated from SEM-EDX, XPS, TGA, FT-IR, and zeta potential detection. The size of particles ranged from 18.7 to 23.7 nm. At the same time, the EDX analysis denoted the existence of several major elements with related percentage values of carbon (52.9%), oxygen (27.6%), molybdenum (8.8%), and nitrogen (4.5%) in the assembled MA@NBAL nanobiosorbent. The effectiveness of MA@NBAL in removing Hg(II) ions was monitored via the batch study method. The optimized maximum removal capacity of Hg(II) ions onto MA@NBAL was established at pH 6.0, 30.0 min equilibrium time, and 20 mg of nanobiosorbent, providing 1444.25 mg/g with a 10.0 mmol/L concentration of Hg(II). Kinetic studies revealed that the adsorption process followed a pseudo-second-order model, with R² values ranging from 0.993 to 0.999 for the two tested Hg(II) concentrations, indicating excellent alignment with the experimental data. This suggests that the chemisorption mechanism involves cation exchange and complex formation. Isotherm model evaluation further confirmed the adsorption mechanism, with the Freundlich model providing the best fit, yielding an R² of 0.962. This result indicates that Hg(II) adsorption onto the surface of MA@NBAL nanobiosorbent occurs on a heterogeneous surface with multilayer formation characteristics. The results of the temperature factor and computation of the thermodynamic parameters referred to endothermic behavior via a nonspontaneous process. Finally, the valid applicability of MA@NBAL nanobiosorbent in the adsorptive recovery of 2.0 and 5.0 µg/mL Hg(II) from contaminated real aquatic matrices was explored in this study, providing 91.2–98.6% removal efficiency. Full article

The removal and detection of highly toxic mercury(II) ions (Hg²⁺) in water used daily is essential for human health and monitoring environmental pollution. Efficient porous organic polymers (POPs) can provide a strong adsorption capacity toward heavy metal ions, although the complex synthetic process and inconvenient phase separation steps limit their application. Hence, a combination of POPs and magnetic nanomaterials was proposed and a new magnetic porous organic polymer adsorbent was fabricated by a green and mild redox reaction in the aqueous phase with trithiocyanuric acid (TA) and its sodium salts acting as reductive monomers and iodine acting as an oxidant. In the preparation steps, no additional harmful organic solvent is required and the byproducts of sodium iodine are generally considered to be non-toxic. The resulting magnetic poly(trithiocyanuric acid) polymers (MPTAPs) are highly porous, have large surface areas, are rich in sulfhydryl groups and show easy magnetic separation ability. The experimental results show that MPTAPs exhibit good adsorption affinity toward Hg²⁺ with high selectivity, rapid adsorption kinetics (10 min), a large adsorption capacity (211 mg g⁻¹) and wide adsorption applicability under various pH environments (pH 2~8). Additionally, MPTAPs can be reused for up to 10 cycles, and the magnetic separation step of MPTAPs is fast and convenient, reducing energy consumption compared to centrifugation and filtration steps required for non-magnetic adsorbents. These results demonstrate the promising capability of MPTAPs as superior adsorbents for effective adsorption and separation of Hg²⁺. Based on this, the prepared MPTAPs were adopted as magnetic solid-phase extraction (MSPE) materials for isolation of trace Hg²⁺ from aqueous samples. Under optimized conditions, the extraction and quantification of trace Hg²⁺ in water samples were accomplished using inductively coupled plasma mass spectrometry (ICP-MS) detection after MSPE procedures. The proposed MPTAPs-based MSPE-ICP-MS method is efficient, rapid, sensitive and selective for the determination of trace Hg²⁺, and was successfully employed for the accurate analysis of trace Hg²⁺ in tap water, wastewater, lake water and river water samples. Full article

This study focuses on the development of new amino-functionalized magnetic Fe₂O₃/SiO₂ nanocomposites with varying silicate shell ratios (1:0.5, 1:1, and 1:2) for the efficient elimination of Hg²⁺ ions found in solutions. The Fe₂O₃/SiO₂–NH₂ adsorbents were characterized for their structural, surface, and magnetic properties using various techniques, including Fourier transform infrared spectrum (FT-IR), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Braunauer–Emmett–Teller (BET), thermogravimetric analysis (TGA), zeta-potential, and particle size measurement. We investigated the adsorption circumstances, such as pH, dosage of the adsorbent, and duration of adsorption. The pH value that yielded the best results was determined to be 5.0. The Fe₂O₃/SiO₂–NH₂ adsorbent with a silicate ratio of (1:2) exhibited the largest amount of adsorption capacity of 152.03 mg g⁻¹. This can be attributed to its significantly large specific surface area of 100.1 m² g⁻¹, which surpasses that of other adsorbents. The adsorbent with amino functionalization demonstrated a strong affinity for Hg²⁺ ions due to the chemical interactions between the metal ions and the amino groups on the surface. The analysis of adsorption kinetics demonstrated that the adsorption outcomes adhere to the pseudo-second-order kinetic model. The study of adsorption isotherms revealed that the adsorption followed the Langmuir model, indicating that the adsorption of Hg²⁺ ions with the adsorbent occurred as a monomolecular layer adsorption process. Furthermore, the thermodynamic analyses revealed that the adsorption of Hg²⁺ ions using the adsorbent was characterized by a spontaneous and endothermic process. Additionally, the adsorbent has the ability to selectively extract mercury ions from a complex mixture of ions. The Fe₂O₃/SiO₂–NH₂ nanocomposite, which is loaded with metal, can be easily recovered from a water solution due to its magnetic properties. Moreover, it can be regenerated effortlessly through acid treatment. This study highlights the potential use of amino-functionalized Fe₂O₃/SiO₂ magnetic nanoparticles as a highly efficient, reusable adsorbent for the removal of mercury ions from contaminated wastewater. Full article