Immobilization Of Metals Research Articles

Sustainable soil rehabilitation with multiple network structures of layered double hydroxide beads: Immobilization of heavy metals, fertilizer release, and water retention

The remediation of heavy metal-contaminated soils necessitated a holistic approach that encompassed water and fertilizer conservation alongside soil property restoration. This study introduced the synthesis of (poly)acrylamide-layered double hydroxide gel spheres (PAM-LDH beads), which were designed to simultaneously immobilize heavy metals, control the release of fertilizers, and enhance soil water retention. Laboratory soil experiments under diverse conditions highlighted the superior performance of PAM-LDH beads in the immobilization of hexavalent chromium (Cr(VI)). The layered double hydroxide (LDH) component was identified as the key player in Cr(VI) immobilization, with anion exchange being the predominant mechanism. Notably, the encapsulated urea within the beads was released independently of environmental influences, governed by a concentration gradient across the beads surface. This release process was characterized by an initial phase of absorptive swelling followed by a diffusive phase. The impact on plant growth was assessed, revealing that PAM-LDH beads significantly curtailed Cr(VI) accumulation and alleviated its phytotoxic effects. Changes in the carbon (C) and nitrogen (N) content of the plants suggested that the urea encapsulated within the beads served as a nutrient source, contributing to soil fertility. Moreover, the water-holding capacity and soil-water characteristic curves of PAM-LDH beads suggested that these superabsorbent beads could delay soil water evaporation. The observed shifts in microbial community structure provided evidence for the enhancement of soil carbon and nitrogen cycles, indicative of improved soil properties.

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.

Comparison and mechanism analysis of MgO, CaO, and Portland cement for immobilization of heavy metals in MSWI fly ash

The significant production of municipal solid waste incineration fly ash (MSWI FA) underscores the importance of developing efficient solidification materials. This study employed MgO and CaO for immobilizing MSWI FA (with a 70% fly ash incorporation), and the immobilization effect was compared with that of Portland cement (PC). Experimental findings revealed that MgO exhibited the most effective stabilization for heavy metals (Cd, Cu, Pb, and Zn) compared to CaO and PC. XRD, FTIR, TG, and SEM analysis indicated that the principal hydration products in MSWI FA binders solidified with MgO, CaO, and PC were Mg(OH)2, CaCO3, and C-S-H gel, respectively. Mg(OH)2 efficiently immobilized heavy metals through chemical complexation and surface adsorption mechanisms. The MgO-treated MSWI FA demonstrated the highest residual fractions and the lowest easily leachable fractions. Moreover, the leaching characteristics of heavy metals were significantly influenced by the pH level, so MgO-treated MSWI FA with a leachate pH of 9.18 achieved the precipitation and stabilization of most heavy metals. In summary, this study provided an effective material selection for MSWI FA immobilization and presented a novel strategy for MSWI FA management.

Biochar with KMnO4-hematite modification promoted foxtail millet growth by alleviating soil Cd and Zn biotoxicity

The excessive accumulation of Cd and Zn in soil poisons crops and threatens food safety. In this study, KMnO4-hematite modified biochar (MnFeB) was developed and applied to remediate weakly alkaline Cd-Zn contaminated soil, and the heavy metal immobilization effect, plant growth, and metal ion uptake of foxtail millet were studied. MnFeB application reduced the phytotoxicity of soil heavy metals; bioavailable acid-soluble Cd and Zn were reduced by 57.79% and 35.64%, respectively, whereas stable, non-bioavailable, residual Cd and Zn increased by 96.44% and 32.08%, respectively. The chlorophyll and total protein contents and the superoxide dismutase (SOD)activity were enhanced, whereas proline, malondialdehyde, the H2O2 content, glutathione reductase (GR), ascorbate peroxidase (APX) and catalase (CAT) activities were reduced. Accordingly, the expressions of GR, APX, and CAT were downregulated, whereas the expression of MnSOD was upregulated. In addition, MnFeB promoted the net photosynthetic rate and growth of foxtail millet plants. Furthermore, MnFeB reduced the levels of Cd and Zn in the stems, leaves, and grains, decreased the bioconcentration factor of Cd and Zn in shoots, and weakened the translocation of Cd and Zn from roots to shoots. Precipitation, complexation, oxidation-reduction, ion exchange, and π-π stacking interaction were the main Cd and Zn immobilization mechanisms, and MnFeB reduced the soil bacterial community diversity and the relative abundance of Proteobacteria and Planctomycetota. This study provides a feasible and effective remediation material for Cd- and Zn-contaminated soils.

Miscanthus sp. root exudate alters rhizosphere microbial community to drive soil aggregation for heavy metal immobilization

The heavy metals (HMs) spatial distribution in soil is intricately shaped by aggregation processes involving chemical reactions and biological activities, which modulate HMs toxicity, migration, and accumulation. Pioneer plants play a central role in preventing HMs at source, yet the precise mechanisms underlying their involvement in soil aggregation remain unclear. This study investigates HMs distribution within rhizosphere and bulk soil aggregates of Miscanthus sp. grown in tailings to elucidate the impact of root exudates (REs) and rhizosphere microbes. The results indicate that Miscanthus sp. enhance soil stability, increasing the proportion of macroaggregates by 4.06 %–9.78 %. HMs tend to concentrate in coarse-aggregates, particularly within rhizosphere environments, while diminishing in fine-aggregates. Under HMs stress, lipids and lipid-like molecules are the most abundant REs produced by Miscanthus sp., accounting for under up to 26.74 %. These REs form complex with HMs, promoting microaggregates formation. Charged components such as sugars and amino acids further contribute to soil aggregation. REs also regulates rhizosphere bacteria and fungi, with Acidobacteriota, Chloroflexi were the dominant bacterial phyla, while Ascomycota and Basidiomycota dominate the fungal community. The synergistic effect of REs and microorganisms impact soil organic matter and nutrient content, facilitating HMs nanoparticle heteroaggregation and macroaggregates formation. Consequently, soil structure and REs shape the distribution of HMs in soil aggregation. Pioneer plants mediate REs interaction with rhizosphere microbes, promoting the distribution of HMs into macroaggregates, leading to immobilization. This study sheds light on the role of pioneer plants in regulating soil HMs, offering valuable insights for soil remediation strategies.

Adsorption of heavy metal ions by carbon-based adsorbent using magnetic nitrogen-doped carbon and graphene oxide

ABSTRACT The adsorption of weighty metal particles from contaminated water sources has garnered significant attention due to its critical role in environmental remediation and ensuring safe drinking water. Heavy metal ions can be removed from water using conventional adsorbents such as activated zeolites; however, these materials have low absorption and slow kinetics. To solve these issues, carbon-based adsorbents that exhibit easy synthesis, high porosity, design ability, and stability have been proposed. In this review, a carbon-based adsorbent, named M-NC, and graphene oxide were created for the particular evacuation of weighty metal particles. To increase the potential for Heavy Metals (HM) immobilization, sulfide-modified biochar was created via a process called synchronous carbon layer epitome. A hypothetical physicochemical and thermodynamic examination of the adsorption of weighty metals Zn2+, Cd2+, Ni2+, Ag2+, Pb2+ and Cu2+ on carbon-based adsorbents was done with factual material science fundaments. The biochar with large surface areas is utilized to eliminate weighty metal particles, quite possibly the most significant heavy metal pollutants, from aqueous solutions. The limit of the adsorbent for eliminating weighty metal ions was concentrated on utilizing Langmuir adsorption isotherm under ultrasound-helped conditions. The Mesoporous Silica Nanoparticles (MNCs) can be applied to the Langmuir model and pseudo-second-order kinetics. It is possible to use the Langmuir and second-order kinetic equations to accurately explain the adsorption method. Thermodynamic limitations were also envisioned because sorption is exothermic when it happens spontaneously. A homogeneous measurable physical science adsorption typically was utilized to describe and analyze the experimental heavy metal removal isotherms at 30°C and pH5 utilizing adsorbents produced by pyrolysis of biomasses (broccoli stalks). The experimental results were investigated in terms of Langmuir and pseudo-2nd-order kinetic equations, Freundlich and isotherm models. The outcome of pH, initial heavy metal ion concentration, contact time, and adsorbent dosage regarding the adsorption capacity and removal efficiency of Pb2+ and Cd2+ on the hydrogel was examined. This study contributes to the advancement of information in the ground of environmentally friendly heavy metal removal techniques, specifically focusing on the usage of biomass-based adsorbents. These findings have the potential to address the need for effective solutions in water purification and environmental cleanup efforts.

Montmorillonite-coupled microbially induced carbonate precipitation (MICP) enhanced contaminant removal and carbon capture in cyanide tailings

Microbial induced carbonate precipitation (MICP) technology is an effective method for immobilization of heavy metals in tailings. However, how to sustainably improve the removal of contaminants and the carbon capture capacity of tailings is a current concern. In this study, montmorillonite-coupled MICP (Mt-MICP) process is proposed to solidify cyanide tailings by improving mineralization properties, heavy metal and cyanide removal, and carbon capture. The results showed that Mt -MICP increased the amount of mineralized precipitation by 0.16–1.33 times; Total cyanide (T-CN) and free cyanide (F-CN) concentrations were reduced by 82.00 and 97.14 %, respectively; Cr, Zn, Cu and Pb leaching concentrations were reduced by 87.18, 42.85, 60.56 and 88.79 %, respectively. Characterizations results such as X-computed tomography (X-CT) confirmed that Mt enhanced the uniformity of the bio-cementation. Furthermore, the Mt-MICP process increased CO2 capture from tailings by 27.15∼34.55 %. Density Functional Theory (DFT) and thermogravimetry (TG) showed that Mt increased the adsorption energy of tailings for CO2 and was converted to CaCO3 by urea catalysis. This work provided new insights into the harmless treatment of CT and microbial carbon capture.

Bamboo biochar helps minimize Brassica phytotoxicity driven by toxic metals in naturally polluted soils of four mine zones

Researchers have recently become interested in utilizing biochar amendment as an organic approach to enhance soil quality and minimize the mobility of toxic metals (TMs), which can help grow TM-tolerant plant species in polluted areas. A pot experiment was conducted to examine the efficacy of bamboo biochar (BB) in reducing the phytotoxicity of four unique mine-contaminated soil types. According to a completely randomized design (CRD), in four replications on Brassica juncea, a five-level bamboo biochar treatment (0 % Control, 2.5 % BB, 5 % BB, 7.5 % BB, and 10 % BB) was administered in naturally contaminated areas of Sarcheshmeh, Gol-Gohar, Chadormalu, and Anguran mines. The data show that Bamboo Biochar (BB) increased soil enzymatic activities (58 %), reformed soil structure, including pH (7 %) and electrical conductivity (EC) (51 %), and decreased the availability of TMs (Zn (37 %), Pb(34 %), Cd(51 %), Cu(34 %)), preventing accumulation in roots (42 %) and translocation to shoots (38 %). The phytochelatin (79 %), ascorbic acid (56 %), glutathione contents (57 %), and antioxidant (51 %) and glyoxalase activities (71 %) in B. juncea ultimately enhanced root-shoot dry biomass (44 %) and overall tolerance to TMs in mine-polluted soil (43 %). BB at 10 % might be used as a reliable soil amendment and natural metal immobilization adsorbent in the soil, as well as a suitable option for reducing oxidative stress caused by TMs in B. juncea plants, which are strong phytoremediation candidates in polluted soils. Future research endeavors might aim to discover cost-effective, efficient, and natural substances that can enhance and diminish environmental toxicity, eliminate soil contamination caused by heavy metals, and ultimately enhance human well-being. Keywords: Biochar Application; Soil amendment; Plant stress tolerance; Toxic metal; Phytoremediation

Heavy metals immobilization of LDH@biochar-containing cementitious materials: Effectiveness and mechanisms

The utilization of tailings for producing solid waste-based concrete can effectively mitigate the environmental consequences stemming from tailings accumulation. However, the presence of high concentrations of heavy metal ions in certain tailings can deleteriously affect the microstructure of the cement matrix. This study investigated the in-situ immobilization performance of Pb2+ and Mn2+ by calcium-aluminum layered double hydroxides (CaAl-LDH) and LDH@biochar blended in cement-based materials. The equilibrium adsorption capacity of CaAl-LDH/LDH@biochar for heavy metals in aqueous solution was assessed by adsorption kinetics, while the effect of pH value on the removal rate of heavy metals was also studied. The workability and mechanical properties of cement mortar are significantly improved with the addition of 4 % LDH@biochar. LDHs@biochar can effectively reduce the deteriorating effects of heavy metal ions on the fundamental properties of cement materials. Compared with CaAl-LDH, the leaching concentrations for Pb2+ and Mn2+ in LDH@biochar at 28 d is decreased by 59 % and 39 %, respectively. The stable adsorption of Pb2+ and Mn2+ by LDH@biochar is attributed to multiple mechanisms, including interlayer anion exchange effect, chemical adsorption of surface functional groups and electrostatic attraction. This study provide valuable insights for enhancing the efficiency of heavy metal immobilization in cement-based materials.

Biochar Blended with Alkaline Mineral Can Better Inhibit Lead and Cadmium Uptake and Promote the Growth of Vegetables.

Three successive vegetable pot experiments were conducted to assess the effects on the long-term immobilization of heavy metals in soil and crop yield improvement after the addition of peanut shell biochar and an alkaline mineral to an acidic soil contaminated with lead and cadmium. Compared with the CK treatment, the change rates of biomass in the edible parts of the three types of vegetables treated with B0.3, B1, B3, B9, R0.2 and B1R0.2 were -15.43%~123.30%, 35.10%~269.09%, 40.77%~929.31%, -26.08%~711.99%, 44.14%~1067.12% and 53.09%~1139.06%, respectively. The cadmium contents in the edible parts of the three vegetables treated with these six additives reduced by 2.08%~13.21%, 9.56%~24.78%, 9.96%~35.61%, 41.96%~78.42%, -4.19%~57.07% and 12.43%~65.92%, respectively, while the lead contents in the edible parts reduced by -15.70%~59.47%, 6.55%~70.75%, 3.40%~80.10%, 55.26%~89.79%, 11.05%~70.15% and 50.35%~79.25%, respectively. Due to the increases in soil pH, soil cation-exchange capacity and soil organic carbon content, the accumulation of Cd and Pb in the vegetables was most notably reduced with a high dosage of 9% peanut shell biochar alone, followed by the addition of a low dosage of 1% peanut shell biochar blended with 0.2% alkaline mineral. Therefore, the addition of a low dosage of 1% peanut shell biochar blended with 0.2% alkaline mineral was the best additive in increasing the vegetable biomass, whereas the addition of 9% peanut shell biochar alone was the worst. Evidently, the addition of 0.2% alkaline mineral can significantly reduce the amount of peanut shell needed for passivating heavy metals in soil, while it also achieves the effect of increasing the vegetable yield.

Layered double hydroxides for simultaneous and long-term immobilization of metal(loid)s in soil under simulated aging

Soil contamination by toxic metals and metalloids poses a grave threat to food security and human well-being. Immobilization serves as an effective method for the remediation of soils contaminated by metal(loid)s. Nevertheless, the ability of soil amendments for simultaneous immobilization of cations and oxyanions, and the long-term effectiveness of immobilization need substantial improvements. In this study, we used a series of layered double hydroxides (LDHs), including Mg-Al LDH and Ca-Al LDH fabricated from pure chemicals, and one waste-derived LDH synthesized using granulated ground blast furnace slag (GGBS), for the immobilization of Cu, Zn, As, and Sb in a historically contaminated soil obscured from a mining-affected region. The LDHs were first subjected to iron (Fe) modification to enhance their short-term immobilization performances toward metal(loid)s. Furthermore, the long-term effectiveness of Fe-modified LDHs was examined via two sets of experiments, including column experiments simulating 2-year water leaching, and accelerated aging experiments simulating 100-year proton attack. It was observed that Fe-modified LDHs, either made from pure chemicals or GGBS, demonstrated promising long-term immobilization performances toward metal(loid)s. Results from this study are encouraging for the future use of LDHs for simultaneous and long-term immobilization of metal(loid)s in soil.

The potential of magnetic biochar prepared by a solvent-free method as a soil amendment: Metal immobilization performance, soil microbial co-occurrence network and community assembly mechanism

Magnetic biochar (MBC) is widely recognized as an effective soil amendment for the immobilization of heavy metals in soils. However, the most commonly used methods currently for manufacturing MBC necessitate the use of iron salt solutions, leading to energy consumption for dehydration and potential environmental risks. Here, we fabricated a magnetic biochar based on the solvent-free method and applied it as a soil passivator at a rate of 5 % (w/w) for 90 days. The metal immobilization performance of MBC was investigated, together with its soil micro-ecological effects including the impacts of MBC application on soil microbial community diversity, composition, co-occurrence network pattern and assembly mechanism. The results showed that MBC treatment significantly decreased the DTPA-extractable Cd and Zn by 54.1 % and 59.5 % (P<0.05) after the 90-day incubation, respectively, higher than that of biochar (BC) treatment (25.6 % for Cd and 50.4 % for Zn). The transformation of Cd, Zn and Pb from labile fractions to residual fraction was facilitated in MBC treatment. Besides, MBC application significantly increased soil pH, soil organic matter content and cation exchange capacity (P<0.05). The addition of MBC considerably altered the soil bacterial community diversity and composition. Both soil environmental variables and bioavailability of metals shaped microbial communities, while the latter explained more. Compared to CK, the complexity and stability of the co-occurrence network in MBC-amended soil were enhanced. Null model analysis implied that the microbial community assembly was governed by the stochastic process in MBC treatment, while the deterministic process was the dominant mechanism initially. Overall, our findings provide insight into the ecological mechanisms and interactions of soil microbial communities in response to MBC application and demonstrate that MBC is a promising amendment for metal-contaminated soil remediation.

Effects of biochar and magnesium oxide on cadmium immobilized by microbially induced carbonate: Mobilization or immobilization in alkaline agricultural soils?

Microbially induced carbonate precipitation (MICP) is a promising technique for remediating heavy metal-contaminated soils. However, the effectiveness of MICP in immobilizing Cd in alkaline calcareous soils, especially when applied in agricultural soils, remains unclear. Biochar and magnesium oxide are two environmentally friendly passivating materials, and there are few reports on the combined application of MICP with passivating materials for remediating heavy metal-contaminated soils. Additionally, the number of treatments with MICP cement and the concentration of calcium chloride during the MICP process can both affect the effectiveness of heavy metal immobilization by MICP. Therefore, we conducted MICP and MICP-biochar-magnesium oxide treatments on agricultural soils collected from Baiyin, Gansu Province (pH = 8.62), and analyzed the effects of the number of treatments with cement and the concentration of calcium chloride on the immobilization of Cd by MICP and combined treatments. The results showed that early-stage MICP could immobilize exchangeable cadmium and increase the residual cadmium content, especially with high-concentration calcium chloride MICP treatment. However, in the later stage, soil nitrification and exchange processes led to the dissolution of carbonate-bound cadmium and cadmium activation. The fixing effect of MICP influence whether the MICP-MgO-biochar is superior to the MgO-biochar. Four treatments with cement were more effective than single treatment in MICP-biochar-magnesium oxide treatment, and the MICP-biochar-magnesium oxide treatment with four treatments was the most effective, with passivation rates of 40.7% and 46.6% for exchangeable cadmium and bioavailable cadmium, respectively. However, attention should be paid to the increase in soil salinity. The main mechanism of MICP-magnesium oxide-biochar treatment in immobilizing cadmium was the formation of Cd(OH)2, followed by the formation of cadmium carbonate.

Immobilization of Heavy Metals by Phosphorus-solubilizing Bacteria and Inhibition of Cd and Pb Uptake by Wheat

Phosphorus-solubilizing microorganisms convert insoluble phosphorus in the soil into phosphorus that can be absorbed by plants. Soluble phosphate combines with heavy metals to form precipitation, reducing the content of available heavy metals, thereby reducing the absorption of heavy metals by crops, which plays an important role in the remediation of heavy metal-contaminated soil. The effects of the immobilization of Cd and Pb and the release of PO43- by the phosphorus-solubilizing bacterium Klebsiella sp. M2 were studied through solution culture experiments. In addition, the effects of strain M2 on wheat uptake of Cd and Pb and its microbiological mechanism were also explored through pot experiments. The results showed that strain M2 reduced the concentrations of Cd and Pb and increased the concentration of PO43- in the solution through cell wall adsorption and induced phosphate precipitation. Pot experiments showed that compared to those in the CK group and inactivated strain M2 group, inoculation with live strain M2 significantly increased （123%-293%） the contents of Ca2-P and Ca8-P in rhizosphere soil, decreased the content of DTPA-Cd （34.48%） and DTPA-Pb （36.72%） in wheat rhizosphere soil, and thus hindered the accumulation of Cd and Pb in wheat grains. Moreover, high-throughput sequencing results showed that strain M2 significantly increased the diversity of wheat rhizosphere bacterial communities； increased the relative abundance of Proteobacteria, Gemmatimonadetes, and Bacteroidota in wheat rhizosphere soil； and increased the proportion of heavy metal-immobilizing and phosphorus-promoting bacteria in wheat rhizosphere soil （mainly Sphingomonas, Nocardioides, Bacillus, Gemmatimonas, and Enterobacter）. These bacterial genera played an important role in immobilizing heavy metals and preventing wheat from absorbing heavy metals. These results provide bacterial resources and theoretical basis for the bioremediation of heavy metal-contaminated farmland.

Novel strategy for efficient energy recovery and pollutant control from sewage sludge and food waste treatment

Considering the high organic matter contents and pollutants in sewage sludge (SS) and food waste (FW), seeking green and effective technology for energy recovery and pollutant control is a big challenge. In this study, we proposed a integrated technology combing SS mass separation by hydrothermal pretreatment, methane production from co-digestion of hydrothermally treated sewage sludge (HSS) centrate and FW, and biochar production from co-pyrolysis of HSS cake and digestate with heavy metal immobilization for synergistic utilization of SS and FW. The results showed that the co-digestion of HSS centrate with FW reduced the NH4+-N concentration and promoted volatile fatty acids conversion, leading to a more robust anaerobic system for better methane generation. Among the co-pyrolysis of HSS cake and digestate, digestate addition improved biochar quality with heavy metals immobilization and toxicity reduction. Following the lab-scale investigation, the pilot-scale verification was successfully performed (except the co-digestion process). The mass and energy balance revealed that the produced methane could supply the whole energy consumption of the integrated system with 26.2 t biochar generation for treating 300 t SS and 120 t FW. This study presents a new strategy and technology validation for synergistic treatment of SS and FW with resource recovery and pollutants control.

Mechanism investigation of food waste compost as a source of passivation agents for inhibiting pyrite oxidation

Pyrite oxidation causes the generation of acid mine drainage (AMD), posing significant challenges in the management of sulfide tailings. Passivation agents such as humic acid have been tested to prevent pyrite oxidation. The potential of using humate rich food waste compost as a source of passivation agents to suppress pyrite oxidation was explored in this study. Batch leaching tests were conducted at room temperature, involved oxidatively leaching a pure pyrite and a pyrite-containing coal refuse sample, respectively, with and without adding the compost at acidic pH. The involved passivation mechanisms were investigated by solution leaching tests and spectroscopic (XPS) and microscopic (SEM) analysis of the pure pyrite sample and its leaching residues. Compared to the control, adding the compost led to the increases in solution pH, removal of the Fe2+/Fe3+ ions from the solutions by adsorption, and remarkable decreases (≥58 %) in sulfur concentration in both samples. Both SEM and XPS analysis indicated that a coating layer was successfully established on pyrite surface after being leached in the presence of the compost. The coating layer comprised a mixture of organic species (e.g., O-CO and N-H/C groups) and phosphate, potentially improving the likelihood of providing antioxidant protection over acidic pH. As a low-cost material, food waste compost can benefit the source control of AMD not only in terms of its surface passivation, but also its intrinsic alkalinity, metal immobilization, and low environmental risk.

Effects of enzyme-induced carbonate precipitation technique on multiple heavy metals immobilization and unconfined compressive strength improvement of contaminated sand

Enzyme-induced carbonate precipitation (EICP) has been studied in remediation of heavy metal contaminated water or soil in recent years. This paper aims to investigate the immobilization mechanism of Zn2+, Ni2+, and Cr(VI) in contaminated sand, as well as strength enhancement of sand specimens by using EICP method with crude sword bean urease extracts. A series of liquid batch tests and artificially contaminated sand remediation experiments were conducted to explore the heavy metal immobilization efficacy and mechanisms. Results showed that the urea hydrolysis completion efficiency decreased as the Ca2+ concentration increased and the heavy metal immobilization percentage increased with the concentration of Ca2+ and treatment cycles in contaminated sand. After four treatment cycles with 0.5 mol/L Ca2+ added, the immobilization percentage of Zn2+, Ni2+, and Cr(VI) were 99.99 %, 86.38 %, and 75.18 %, respectively. The microscale analysis results presented that carbonate precipitates and metallic oxide such as CaCO3, ZnCO3, NiCO3, Zn(OH)2, and CrO(OH) were generated in liquid batch tests and sand remediation experiments. The SEM-EDS and FTIR results also showed that organic molecules and CaCO3 may adsorb or complex heavy metal ions. Thus, the immobilization mechanism of EICP method with crude sword bean urease can be considered as biomineralization, as well as adsorption and complexation by organic matter and calcium carbonate. The unconfined compressive strength of EICP-treated contaminated sand specimens demonstrated a positive correlation with the increased generation of carbonate precipitates, being up to 306 kPa after four treatment cycles with shear failure mode. Crude sword bean urease with 0.5 mol/L Ca2+ added is recommended to immobilize multiple heavy metal ions and enhance soil strength.

Structural studies of calcium silicate hydrate modified with heavy metal cations

This study investigates the immobilization mechanisms of heavy metal ions in the C-S-H phase. Synthetic C-S-H phases were prepared via the precipitation method, incorporating five different ions (Pb(II), Cd(II), Ni(II), Zn(II), and Cr(III)). Structural analysis of the obtained material was conducted using vibrational spectroscopy (both FT-IR and Raman), X-ray photoelectron spectroscopy, and X-ray diffraction. Spectroscopic methods were primarily employed to evaluate the structural effects and polymerization degree of the resulting C-S-H phase. Morphological changes were characterized using scanning and transmission electron microscopy (SEM and TEM, respectively). Our findings reveal several mechanisms for immobilizing heavy metal cations: precipitation of insoluble compounds (particularly notable for Ni(II) and Cr(III)), replacement of Ca(II) ions within the silicate structure (evident in the crystallization of Ca(OH)2 in samples containing Cd(II), Ni(II), and Zn(II) in minimal quantities), and strong bonding of certain metals (such as Pb(II)) with the C-S-H phase structure. These insights contribute to understanding the potential applications of C-S-H phases in heavy metal immobilization.

Isolation of biocrust cyanobacteria and evaluation of Cu, Pb, and Zn immobilisation potential for soil restoration and sustainable agriculture

Soil contamination by heavy metals represents an important environmental and public health problem of global concern. Biocrust-forming cyanobacteria offer promise for heavy metal immobilisation in contaminated soils due to their unique characteristics, including their ability to grow in contaminated soils and produce exopolysaccharides (EPS). However, limited research has analysed the representativeness of cyanobacteria in metal-contaminated soils. Additionally, there is a lack of studies examining how cyanobacteria adaptation to specific environments can impact their metal-binding capacity. To address this research gap, we conducted a study analysing the bacterial communities of cyanobacteria-dominated biocrusts in a contaminated area from South Sardinia (Italy). Additionally, by using two distinct approaches, we isolated three Nostoc commune strains from cyanobacteria-dominated biocrust and we also evaluated their potential to immobilise heavy metals. The first isolation method involved acclimatizing biocrust samples in liquid medium while, in the second method, biocrust samples were directly seeded onto agar plates. The microbial community analysis revealed Cyanobacteria, Bacteroidota, Proteobacteria, and Actinobacteria as the predominant groups, with cyanobacteria representing between 13.3 % and 26.0 % of the total community. Despite belonging to the same species, these strains exhibited different growth rates (1.1–2.2 g L−1 of biomass) and capacities for EPS production (400–1786 mg L−1). The three strains demonstrated a notable ability for metal immobilisation, removing up to 88.9 % of Cu, 86.2 % of Pb, and 45.3 % of Zn from liquid medium. Cyanobacteria EPS production showed a strong correlation with the removal of Cu, indicating its role in facilitating metal immobilisation. Furthermore, differences in Pb immobilisation (40–86.2 %) suggest possible environmental adaptation mechanisms of the strains. This study highlights the promising application of N. commune strains for metal immobilisation in soils, offering a potential bioremediation tool to combat the adverse effects of soil contamination and promote environmental sustainability.

The role of soil structure on the cracking and cadmium leaching behavior of biochar-amended fine-grained soils

Biochar has shown promising potential for soil remediation, yet its impact on heavy metals (HMs) immobilization often overlooks soil structure, which could influence soil cracking behavior and HMs transport. To address this gap, this study investigates the role of soil structure (dry density and aggregate size) on the cracking and cadmium (Cd) leaching behavior of biochar-amended fine-grained soils. A series of semi-dynamic leaching tests were conducted on samples with and without wetting-drying (W-D) cycles. Based on the proposed improved method for quantifying the effective diffusion coefficient (De) of Cd in unsaturated soils and microstructural analyses, we found that: (1) Higher dry density and larger aggregate generally resulted in smaller De by decreasing soil pore volume. (2) Biochar could connect isolated pores within large aggregates through its internal pores, yielding greater increases in De (294.8%–469.0%) compared to small aggregates (29.1%–77.4%) with 3% biochar. However, further increases in biochar dosage led to decreased De, primarily due to the dense pore structure. (3) Biochar effectively inhibited soil cracking, achieving the highest reduction of 36.8% in surface crack ratio. (4) After W-D cycles, samples exhibited higher De with increasing dry density, with aggravated cracking being the primary cause, suggesting preferential flow within the cracks, particularly those penetrating the soil. This study highlights the importance of careful consideration of soil structure and cracking potential before in situ field application of biochar as a remediation agent for HMs-contaminated fine-grained soils.