Search Results (30)

Acidic mine drainage (AMD) poses a severe global environmental threat due to its high acidity and elevated levels of toxic hexavalent chromium (Cr(VI)), for which biogenic iron sulfide (FeS) nanoparticles have emerged as a promising remediation agent; however, their practical application is hindered by aggregation and oxidative deactivation. This research synthesized biogenic FeS nanoparticles via sulfate-reducing bacteria (SRB) and employed humic acid (HA) as a stabilizing agent to enhance Cr(VI) removal performance in simulated AMD conditions. Single-factor experiments combined with response surface methodology identified the optimal biosynthetic conditions for FeS: yeast extract powder dosage of 2.2 g/L, Fe/S molar ratio of 0.8, and NH₄Cl dosage of 3.1 g/L. Under these conditions, the material achieved 84.25% Cr(VI) removal, with the Fe/S molar ratio identified as the most influential parameter governing synthesis and performance. Introducing HA at an optimal dosage of 2 mg/L drove marked improvements in both nanoparticle yield and reactivity: FeS yield increased to 1096.26 mg/L, Cr(VI) removal efficiency reached 99.62%, and residual Cr(VI) dropped from 15.75 mg/L to just 0.38 mg/L. Kinetic and isotherm analyses, paired with SEM/TEM imaging and zeta potential measurements, revealed that HA stabilization improved particle dispersion and reduced lamellar stacking, resulting in a surface-controlled Cr(VI) removal process. FTIR and 2D-COS analyses demonstrated that HA-derived oxygen-containing functional groups, including O–H/N–H, C=O, and C–O moieties, played a central role in interfacial interactions during Cr(VI) sequestration. XRD results confirmed that Cr(VI) was reduced to Cr(III) and primarily immobilized as low-solubility CrOOH and Cr₂S₃, while the formation of Fe–Cr spinel-like phases remains tentative without X-ray Photoelectron Spectroscopy (XPS) validation. Further investigation via surface-sensitive spectroscopy and dynamic leaching tests is needed to fully assess the long-term stability of the reaction products. Full article

Developing adsorbents that combine high capacity with structural robustness remains a critical challenge for dye wastewater treatment. In this study, we propose a “pollutant-induced gelation” strategy to address this limitation, using Fe(III)-activated palygorskite nanorod aggregates as a model system for the highly efficient sequestration of Congo red (CR). Unlike conventional modification methods that rely solely on surface functionalization, this approach leverages the adsorbed dye itself as a synergistic assembly promoter. The addition of CR significantly consolidates the Fe(III)-mediated aggregation of palygorskite nanorods, leading to the formation of an integrated three-dimensional porous network with distinct gel-like rheological behavior. This dye-induced gel network not only provides abundant confined spaces for pollutant entrapment but also enhances the structural integrity of the adsorbent, facilitating separation and potential reuse. Compared to pristine palygorskite, the Fe(III)-activated material exhibited a 95.4–277% increase in adsorption capacity across a pH range of 4–10. The adsorption process followed pseudo-second-order kinetics and the Temkin isotherm model, and was thermodynamically spontaneous and exothermic. Mechanistic studies revealed a synergistic interplay: Fe(III) served as primary cross-linking nodes to construct the network framework, while CR molecules acted as inducers to reinforce the gel architecture, enabling strong physical immobilization of dye aggregates. This work provides a new paradigm for designing intelligent, gel-based adsorbents from natural nanoclays, transforming a pollutant into a structural promoter. Full article

This study investigates the preparation of a composite material by immobilizing Bacillus subtilis on biochar derived from chicken manure biogas residue for the removal of Cr(VI) from wastewater. The results demonstrated that the composite material (Bacillus subtilis immobilized biochar, BIB) achieved a maximum Cr(VI) removal efficiency of 94.1% in a 100 mg/L Cr(VI) solution within 4 h. The chicken manure-derived biochar not only served as an effective carrier for Bacillus subtilis but also enhanced the Cr(VI) removal efficiency through a synergistic effect with the microorganism. Functional groups such as phosphorus, carboxyl, and hydroxyl groups on the biochar surface played a key role in the sorption of Cr(VI). Bacillus subtilis primarily reduced Cr(VI) to Cr(III) by secreting cellular reductases. The combined action of biochar and Bacillus subtilis increased the Cr(VI) removal rate by 13.71% compared to biochar alone. This study presents a promising approach for Cr(VI) remediation in contaminated water and lays a theoretical foundation for the development of composite materials for Cr(VI) reduction. Full article

Hazardous galvanic sludge waste (GSW) from the electroplating industry, produced at 100,000–150,000 tonnes/year in the EU and containing high concentrations of Cr and Ni was successfully treated using metakaolin-based geopolymers via Stabilization/Solidification (S/S). The experimental design incorporated chelating (sodium diethyl dithio carbamate, C₅H₁₀NS₂Na, DTC), reducing (sodium sulfide, Na₂S), and adsorbing (hydroxyapatite, Ca₅(PO₄)₃(OH), Hap) agents separately to improve heavy metal immobilization. The results demonstrated that Na₂S drastically decreased Cr release by −98.7% by reducing mobile Cr(VI) to insoluble Cr(III). DTC reduced Ni leaching by −93.4%, forming sparingly soluble Ni(II)(DTC)₂ complexes that precipitated within the matrix. Hap enhanced Ni retention by 55.5% via cation exchange but was ineffective for Cr due to electrostatic repulsion with the anion Cr(VI)O₄²⁻ at the geopolymer’s high pH. This work is the first to apply geopolymerization coupled with these chemical agents for S/S of as-received galvanic waste, offering a highly efficient, low-carbon strategy to manage this hazardous industrial residue. Full article

The large-scale and high-value utilization of industrial solid waste has become a key research area in sustainable building materials. However, ensuring effective backfilling quality in narrow or irregular spaces remains challenging in civil engineering. Developing flowable solidification materials from industrial solid waste not only resolves issues inherent in traditional backfilling techniques but also enhances efficient resource utilization. In this study, phosphogypsum was used to prepare geopolymers, which served as binders replacing cement in producing phosphogypsum-based fluidized solidified soil (PFSS). The workability, mechanical strength, and toxic substance leaching of PFSS were evaluated. Moreover, the underlying mechanisms of strength formation and toxic substance immobilization were investigated. The optimal PFSS composition was determined to have a water-to-solid ratio of 0.48–0.50 and a geopolymer content of 12–18% (by mass). Under these conditions, the material exhibited fluidity ranging from 160 to 220 mm, a 28-day compressive strength of 0.86 MPa, a California Bearing Ratio (CBR) of 8%, and a resilient modulus of 40 MPa. These parameters satisfy the performance standards required for backfilling in high-grade highways. The leaching concentrations of heavy metals (As, Pb, and Cr) complied with China’s Class III groundwater quality standards. Microstructural analyses indicated the occurrence of hydration, pozzolanic reactions, geopolymerization, and carbonation. Microstructural analyses indicated the formation of an interlocking three-dimensional network, composed of C-S-H, C-A-S-H gels, and ettringite (AFt), which contributes significantly to the strength development and immobilization of heavy metals. These products collectively formed an interlocking three-dimensional network structure, significantly contributing to PFSS strength development. Heavy metals were effectively immobilized within the matrix due to the combined effects of physical adsorption and chemical bonding. Full article

Ore mining and smelting are often related to environmental pollution. This study provides information about the geochemical features of Technosols at historical mining and metallurgical sites in the Tatra Mountains, southern Poland, evaluating the contents of potentially toxic trace elements (PTTE) and their behaviours in soils, as well as the influence of soil properties on PTTE mobility. Thirteen soil profiles were studied in eight abandoned mining and smelting sites. PTTE concentrations, including rare earth elements (REE), were measured using ICP-MS and ICP-OES. Selected elements (Cu, Zn, Pb, Cd, As, Sb, Ba, Sr, Co, Ni, Mn and Cr) were fractionated using the modified European Community Bureau of Reference (BCR) four-step sequential extraction. Contamination of soils with PTTE was compared against Polish regulatory limits, which were exceeded for Cu, Zn, Pb, Mo, Hg, As, Co, Ni and Ba, with concentrations exceeding limits by 16, 18, 34 and 160 times for Cu, Hg, As and Ba, respectively, in some profiles. Based on geochemical features depending on parent material properties, the soils examined were divided into three groups. Group I Technosols (near-neutral soils developed from Fe/Mn-ore and carbonate-bearing mining waste) were particularly enriched in Co, Ni, Mn and REE. Group II Technosols (acidic soils developed from polymetallic ore-bearing aluminosilicate mining waste) contained elevated concentrations of Cu, Zn, Hg, As, Sb, Bi, Co, Ag, Ba, Sr, U and Th; they contained lower contents of REE than Group I Technosols. Group III Technosols (soils developed in smelting-affected areas and containing metallurgical waste) were rich in Cu, As, Sb, Ba, Hg, Co and Ag and contained the lowest REE contents among the studied soils. Sequential BCR extraction revealed that PTTE mobility varied strongly according to soil group, with higher mobility of Mn, Cu and Zn in acidic polymetallic ore-derived soils (Group II), while carbonate-rich soils (Group I) showed mainly immobile forms. Metallurgical slag-derived soils (Group III) exhibited complex PTTE behaviour controlled by organic matter and Fe/Mn oxides. Soil properties (pH, carbonates and TOC) seem to control PTTE mobility. Full article

Microbial remediation of Cr(VI)-polluted wastewater offers an effective and sustainable green method. In this study, a novel strain Priestia megaterium strain BM.1 that was capable of reducing Cr(VI) was domesticated. In order to improve its Cr(VI) reduction and adsorption performance, calcium-modified hydrochar (HC-Ca) was utilized to immobilize the strain to obtain the composite material BM.1-Ca. The BM.1-Ca composite achieved a Cr(VI) removal efficiency of 97% at an initial concentration of 60 mg/L within 60 h, representing a 1.96-fold enhancement compared to BM.1 alone and demonstrating significantly improved microbial Cr(VI) removal capacity. The addition of HC-Ca was instrumental in maintaining the stable Cr(VI) removal efficiency of BM.1 in the presence of altered incubation environments and interference from co-existing ions. The reduction in Cr(VI) by BM.1 and the immobilization of Cr(III) on the surface of BM.1-Ca are the main removal mechanisms of Cr(VI). Analysis of microbial oxidative stress and extracellular polymers showed that HC-Ca was able to attenuate the oxidative stress of BM.1 as well as promote the secretion of extracellular polymers. This study reveals the intrinsic mechanism of the novel material BM.1-Ca for remediation of Cr(VI) pollution in water bodies and provides an effective method for bioremediation of Cr(VI). Full article

To address the challenges of environmental adaptability and passivation in nanoscale zero-valent iron (nFe⁰) systems, we developed oxalate-modified nFe⁰ (nFe_oxa) through a coordination-driven synthesis strategy, aiming to achieve high-efficiency Cr(VI) removal with improved stability and reusability. Structural characterization (STEM and FT-IR) confirmed the formation of a FeC₂O₄/nFe⁰ heterostructure, where oxalate coordinated with Fe(II) to construct a semiconductor interface that effectively inhibits anoxic passivation while enabling continuous electron supply, achieving 100% Cr(VI) removal efficiency within 20 min at an optimal oxalate/Fe molar ratio of 1/29. Mechanistic studies revealed that the oxalate ligand accelerates electron transfer from the Fe⁰ core to the surface via the FeC₂O₄-mediated pathway, as evidenced by EIS and LSV test analyses. This process dynamically regenerates surface Fe(II) active sites rather than relying on static-free Fe(II) adsorption. XPS and STEM further demonstrated that Cr(VI) was reduced to Cr(III) and uniformly co-precipitated with Fe(II/III)-oxalate complexes, effectively immobilizing chromium. The synergy between the protective semiconductor layer and the ligand-enhanced electron transfer endows nFe_oxa with superior reactivity. This work provides a ligand-engineering strategy to design robust nFe⁰-based materials for sustainable remediation of metal oxyanion-contaminated water. Full article

A stabilized biochar (BC)–nano-scale zero-valent iron (nZVI) composite (BC-nZVI@Cell-g-PAA) was prepared using cellulose-grafted polyacrylic acid (Cell-g-PAA) as the raw material through in situ polymerization and liquid-phase reduction methods for the remediation of hexavalent chromium (Cr(VI))-contaminated water. BC-nZVI@Cell-g-PAA was characterized by XRD, FT-IR, SEM, BET, TEM, and XPS. According to the batch experiments, under optimized conditions (Cr(VI) concentration of 50 mg/L, pH = 3, and dosage of 2 g/L), the BC-nZVI@Cell-g-PAA composite achieved maximum Cr(VI) removal efficiency (99.69%) within 120 min. Notably, BC, as a carrier, achieved a high dispersion of nZVI through its porous structure, effectively preventing particle agglomeration and improving reaction activity. Simultaneously, the functional groups on the surface of Cell-g-PAA provided excellent protection for nZVI, significantly suppressing its oxidative deactivation. Furthermore, the composite effectively reduced Cr(VI) to insoluble trivalent chromium(Cr(III)) species and stabilized them on its surface through immobilization. The synergistic effects of physical adsorption and chemical reduction greatly contributed to the removal efficiency of Cr(VI). Remarkably, the composite exhibited excellent reusability with a removal efficiency of 62.4% after five cycles, demonstrating its potential as a promising material for remediating Cr(VI)-contaminated water. In conclusion, the BC-nZVI@Cell-g-PAA composite not only demonstrated remarkable efficiency in Cr(VI) removal but also showcased its potential for practical applications in environmental remediation, as evidenced by its sustained performance over multiple reuse cycles. Moreover, Cr(VI), a toxic and carcinogenic substance, poses significant risks to aquatic ecosystems and human health, underscoring the importance of developing effective methods for its removal from contaminated water. Full article

The mining and processing of coal resources generate substantial coal-based solid wastes, such as coal gangue and slag, which pose environmental challenges, occupy land, and are difficult to manage. However, utilizing these wastes for the stabilization and solidification (S/S) of municipal sludge containing chromium (Cr) and nickel (Ni) offers an effective solution for mitigating environmental and groundwater pollution while enabling sustainable waste treatment and resource utilization. This study applied an alkali-activated coal gangue–S95 granulated blast furnace slag-based binder (CGS) to the S/S treatment of municipal sludge. The effects of the liquid-to-solid ratio, alkali activator dosage, sludge content, and incineration on compressive strength and the leaching of Cr and Ni were analyzed. The results showed that compressive strength decreased with increases in the sludge content and liquid-to-solid ratio, while incinerated sludge (ESA) samples exhibited better strength than raw sludge (ES). Incineration decomposed the calcite (CaCO₃) into CaO, which facilitated the oxidation of Cr(III) to Cr(VI) and increased Cr leaching in the ESA. However, the ESA samples demonstrated superior heavy metal stabilization, as CGS reduced Cr(VI) to Cr(III) and immobilized it through the formation of chromite phases. Using ESA as a binder in CGS provides a safe, efficient approach for resource recovery and heavy metal stabilization, offering a novel solution for the environmental management and utilization of coal-based solid wastes. Full article

The complex environmental conditions at Cr-contaminated sites, characterized by uneven ion distribution, oxidants competition, and limited solid-phase mobility, lead to inadequate mixing of Fe-based reducing agents with Cr, posing significant challenges to the effectiveness of Cr remediation through Cr-spinel precipitation. This study investigates the distinct roles of Fe(II), Fe(III), and Cr(III) in Cr-spinel crystallization under ambient temperature and pressure. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray absorption near-edge structure spectroscopy, and Mössbauer spectroscopy were employed to elucidate the phase composition, microstructure, and ion coordination within the precipitates. Our findings indicate that Fe(II) acts as a catalyst in the formation of the spinel phase, occupying octahedral sites within the spinel structure. Under the catalytic influence of Fe(II), Fe(III) transitions into the spinel phase, occupying both the tetrahedral and the remaining octahedral sites. Meanwhile, Cr(III), due to its high octahedral site preference energy, preferentially occupies the octahedral sites. When Fe(II) or Fe(III) is present but does not meet the ideal stoichiometric ratio, a deficiency in Fe(II) leads to low yield and poor crystallinity of Cr-spinel, whereas a deficiency in Fe(III) can completely inhibit its formation. Conversely, when either Fe(II) or Fe(III) is in excess, the formation of Cr-spinel remains feasible. Furthermore, metastable Cr phases can be transformed into stable Cr-spinel by adjusting the Fe(II)/Fe(III)/Cr(III) ratio. These results highlight the broad range of conditions under which Cr-spinel mineralization can occur in environmental settings, enhancing our understanding of the mechanisms driving Cr-spinel formation in Cr-contaminated sites treated with Fe-based reducing agents. This research provides critical insights for optimizing Cr remediation strategies. Full article

Nanocomposites (NCs) consisting of zero-valent iron nanoparticles (nZVI) immobilized in chitosan (CS) were prepared and employed for the removal of hexavalent chromium (Cr(VI)) from both synthetic and real wastewater. Medium (MCS)- and high (HCS)-molecular-weight chitosan and stabilization with carboxymethylcellulose (CMC) and different nZVI loads were explored. Characterization through scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDS) and X-ray diffraction (XRD) revealed millimeter-sized spheres with micrometer-sized nZVI clusters randomly distributed. Better nanoparticle dispersion was observed in NCs from the CMC-MCS and HCS combinations. Fourier-transform infrared spectroscopy (FTIR) analysis indicated that CS binds to Fe(II) or Fe(III) on the surface of nZVI through its functional groups -CONH-, -N-H, and -C-OH and through the -${\mathrm{COO}}^{-}$ functional group of CMC, forming a bidentate bridge complex. Through experiments with synthetic waters, it was found that the elimination of Cr(VI) was favored by lowering the pH, obtaining the maximum percentage of Cr(VI) removal at pH 5.5. With real waters, it was shown that increasing the mass of NCs also improved the removal of Cr(VI), following a pseudo-second-order adsorption kinetics. The synthesized materials show great potential for applications in environmental remediation, showing good efficiency in the removal of Cr(VI) in wastewater. Full article

Current studies of chromium adsorption kinetics at the solid–liquid interface often neglect the influence of coexisting ions in complex wastewaters. Thus, it is critical to explore the hexavalent chromium Cr(VI) adsorption kinetics of solid-phase brucite (Mg(OH)₂) in liquid-phase wastewater containing coexisting aluminum ions (Al(III)). This paper reveals that the presence of Al(III) significantly enhanced the Cr(VI) adsorption efficiency onto Mg(OH)₂, with a peak of up to 91% compared to 5% for the absence of Al(III). The main reason for this enhancement was the initial surface ternary complexation of Mg(OH)₂ and the cationic (Al(III)) isomorphic substitution to form Mg(II)-Al(III) layered double hydroxides (LDH), which also indicates a solid-phase transition on the surface of Mg(OH)₂, which led to electrostatic adsorption in the gallery and made Cr(VI) immobilized and not readily released. Further calculation and analysis of the adsorption energy confirmed the mechanism of Cr(VI) adsorption. It was also concluded that Cr(VI) migration in Mg(OH)₂-containing minerals was affected by the phase transformation of solids in the presence of Al(III). Hence, this study not only reveals the adsorption mechanism during the treatment of composite pollutant wastewater but also provides the methodological reference for brucite synergistic adsorption to remove heavy metal ions and purify and treat complex polluted wastewater. Full article

Plants of the Ambrosia genus are invasive and cause many ecological problems, including the oppression of the growth of agricultural crops and native plants, land depletion, and the production of strong allergens. The use of weeds as a sustainable feedstock for biogas production, either methane or hydrogen, is a promising way to fulfill the energy needs of the current generation, eliminate the depletion of non-renewable carbon resources, and preserve the ecosystem degradation caused by invasive species impacts. A diversified microbial community was used as inoculum and Ambrosia artemisiifolia L. biomass as a substrate for anaerobic degradation and methane production. In this regard, the development of biotechnological approaches to ragweed degradation will promote the integration of new renewable energy systems. Herein, we have shown the high effectiveness of combining the processes of anaerobic degradation of plant biomass for methane production and detoxification of meal-containing model sewage by a diversified microbial community. Thus, the maximum methane yield was 56.0 L kg⁻¹ TS. The presence of 500 mg L⁻¹ Cu(II) slightly inhibited methane synthesis, and the methane yield was 38.4 L kg⁻¹ TS. In contrast to a diversified microbial community, the natural microbiome of ragweed almost did not synthesize methane and did not degrade plant biomass (Kd = 2.3). Methanogens effectively immobilized Cr(IV), Cu(II), and Fe(III) during ragweed fermentation at initial concentrations of 100–200 mg L⁻¹. The obtained results showed the high effectiveness of applying a diversified microbial community in a sewage treatment plant for the degradation of a noxious plant, Ambrosia artemisiifolia L. Full article

Hexavalent chromium (Cr(VI)) is a highly mobile cancerogenic and teratogenic heavy metal ion. Among the varied technologies applied today to address chromium water pollution, photocatalysis offers a rapid reduction of Cr(VI) to the less toxic Cr(III). In contrast to classic photocatalysts, Metal-Organic frameworks (MOFs) are porous semiconductors that can couple the Cr(VI) to Cr(III) photoreduction to the chromium species immobilization. In this minireview, we wish to discuss and analyze the state-of-the-art of MOFs for Cr(VI) detoxification and contextualizing it to the most recent advances and strategies of MOFs for photocatalysis purposes. The minireview has been structured in three sections: (i) a detailed discussion of the specific experimental techniques employed to characterize MOF photocatalysts, (ii) a description and identification of the key characteristics of MOFs for Cr(VI) photoreduction, and (iii) an outlook and perspective section in order to identify future trends. Full article