Filter cake is one of the main waste products of zinc processing industries and it contains a high amount of toxic heavy metals. In this research in order to reduce heavy metals leachability in filter cake, Portland cement, natural pozzolan, diammonium phosphate (DAP), triple superphosphate (TSP), lime, zinc oxide and ground granulated blast furnace slag (GGBFS) have been used. This research’s results suggest that even though leachability of lead in the filter cake is quite low, it should be noted that limestone doubles the solubility level of Pb due to the mineralogical nature of the waste, by converting its sulphate form (PbSO4) to its carbonate form (PbCO3), which is more soluble. TSP was the only additive capable of reducing the leachability of metal elements in the filter cake as well as stabilizing the amounts of Pb and Cd in TCLP extracts within the limit. Although all additives were able to reduce Cd leachability, TSP and ZnO had the most remarkable efficiency. According to XRD results, the main factor in lead stabilization using TSP was a reduction in the amount of PbSO4 (with high Ksp) and an increase in PbS (with low Ksp), which ultimately reduced lead leachability. The Pozzolan which was used for the first time as a stabilizer demonstrated a good performance in reducing the leachability of Cd, Ni and Cu. In addition, due to the pseudo-cementitious properties of Pozzolan, it can reduce leachability of metal elements, along with other additives such as cement, by increasing the solidification efficiency.

The reaction of Pd(II) with 1,8-dihydroxy-2-(pyrazol-5-ylazo)-naphthalen-3,6-disulphonic acid immobilized by physical sorption onto Dowex 1-X8 ion-exchange resin was investigated with the aim to develop the sorption-spectroscopic test method for the detection of low Pd(II) concentrations in water. The resin phase absorption spectra of the reagent and its Pd(II) complex were followed. The immobilized reagent has the spectral characteristics similar to those in the water and forms with Pd(II) 1:1 complex with the absorption maximum at 650 nm. Parameters, such as pH, wavelength and contact time have been optimized for a given amount of the sorbed reagent. The experimental conditions for the linear dependence of absorbance vs. Pd(II) concentration have been determined.

In acidic medium, hazardous heavy metals of lead-zinc tailing (LZT) are easily leachable and mobilizable. Thus, the hazard, amount, form, and complexity of the leached heavy metals under acidic precipitation become a major environmental concern. This work investigates the gangue minerals, toxicity, speciation, leaching characteristics of heavy metals in LZT under simulated acid rain, as well as immobilization effects and mechanisms using a sustainable binder. In LZT, dolomite, quartz, calcite, and muscovite are the main gangue minerals, tiny hazardous metallic minerals were absorbed in the surface. The results revealed that Pb, Zn, Cr, and Cd were the predominant harmful elements, particularly Pb and Zn. Zn is leached completely and is the concerned hazardous element under simulated acid rain. In the acid rain neutralization ability test, the amount of leachable Pb, Cr, Ca, and Si maintained in equilibrium, leached Zn, Cd, Al, and Mg depended on the addition of acid. Pb and Ca were sedimented in residues. Immobilization of Pb, Zn, Cr, and Cd depended on the stability of Ca(OH)₂/C–S–H of hydrates, and 70% LZTHP after curing 7 days can be used for some practical engineering projects. This work opens up deeply understandings for the leached heavy metals under acidic precipitation and improves the sustainable and safe in the field of immobilization of heavy metals.

Soil heavy metal contamination has increasingly become a serious environmental issue globally, nearing crisis proportions. There is an urgent need to find environmentally friendly materials to remediate heavy-metal contaminated soils. With the continuing maturation of research on using biochar (BC) for the remediation of contaminated soil, nano-biochar (nano-BC), which is an important fraction of BC, has gradually attracted increasing attention. Compared with BC, nano-BC has unique and useful properties for soil remediation, including a high specific surface area and hydrodynamic dispersivity. The efficacy of nano-BC for immobilization of non-degradable heavy-metal contaminants in soil systems, however, is strongly affected by plant rhizosphere processes, and there is very little known about the role that nano-BC play in these processes. The rhizosphere represents a dynamically complex soil environment, which, although having a small thickness, drives potentially large materials fluxes into and out of plants, notably agricultural foodstuffs, via large diffusive gradients. This article provides a critical review of over 140 peer-reviewed papers regarding nano-BC-rhizosphere interactions and the implications for the remediation of heavy-metal contaminated soils. We conclude that, when using nano-BC to remediate heavy metal-contaminated soil, the relationship between nano-BC and rhizosphere needs to be considered. Moreover, the challenges to extending our knowledge regarding the environmental risk of using nano-BC for remediation, as well as further research needs, are identified.

The tannery industries utilize environmentally hazardous chemicals to achieve dehairing of animal hides, which causes enormous waterbed pollution & high TDS load. Alkaline protease enzyme for dehairing can be an effective solution to resolve the environmental problems of the tannery industry waste. However, stable, cost-efficient and eco-benign formulations of alkaline protease need to be developed for commercial applications in the tannery industry. This works aimed at development of a nano-formulation of the enzyme alkaline protease (AKP) as a bioconjugate nano silica-alkaline protease enzyme (BC–SiNP-AKP). This work reports one pot green synthesis of the BC-SiNP-AKP bionanoconjugate complex which included both biotemplating and immobilization of the AKP on to the synthesized silica nanoparticles from cell-free extracts of Bacillus circulans grown in potato peel based medium. Among the cell free crude, acetone concentrated and purified sols of the enzyme AKP, acetone precipitated enzyme sol was found to be best for the biological SiNP synthesis and formation of BC-SiNP-AKP conjugate. The BC-SiNP-AKP had size ranging from 100 to 200 nm with crystalline morphologies varying from spherical, tubular to laminated crystallites. The developed bioconjugate formulation displayed 1.7-fold increase in the enzyme activity post nano-conjugation with superlative dehairing potential on goat skin. The optimized parameters for dehairing were found to be as temperature 37 °C for 24 h of incubation and with enzyme to buffer ratio (2: 50 mL). Thereafter, the dehaired skin was assessed for its histopathological effects, which were found to be safe without any deteriorative changes. The developed formulation is environmentally congenial for its use as depilating agent for animal hides in terms of being green, single pot and cost effective synthesis.

Water contamination caused by radionuclides is a major environmental issue. Uranium (U) belongs to the actinide group of elements. Hexavalent uranium (U(VI)) is radioactively and chemically harmful and highly mobile in the environment and wastewater stream. Therefore, developing highly efficient materials for minimizing the environmental impact of U(VI) is essential. To achieve this goal, we successfully synthesized a novel material, namely graphene oxide (GO)/hydroxyapatite (HAP), by directly assembling GO and HAP through a facile hydrothermal method, which exhibits effective U(VI) removal and immobilization. The GO/HAP composite has an outstanding sorption capacity for U(VI) (i.e., 373.00 mg/g) within 5 min at a pH of 3.0. The parameters from thermodynamic analysis indicated that the GO/HAP composite absorbed U(VI) through a process of spontaneous and exothermic adsorption. XPS, XRD, and FT-IR results revealed that the composite’s phosphate group was mainly responsible for U(VI) retention and incorporation. The GO/HAP composite’s enhanced U(VI) sorption capacity is most likely ascribed to the synergistic effect after functionalizing with nano HAP. The current findings may greatly facilitate the creation of rational design strategies to develop highly efficient materials that can treat radioactive wastewater.

Mixed pollution due to heavy metals (HMs), especially cadmium (Cd), lead (Pb), and arsenic (As), seriously endangers the safety of food produced in paddy soil. In the field experiments, foliar application of 2,3-dimercaptosuccinic acid (DMSA) at the flowering stage was found to significantly reduce the levels of Cd, Pb, total As, and inorganic As (iAs) in rice grains by 47.95%, 61.76%, 36.37%, and 51.24%, respectively, without affecting the concentration of metallonutrients, including Mn, K, Mg, Ca, Fe, and Zn. DMSA treatment significantly reduced the concentrations of Cd, Pb, and As in the panicle node, panicle neck, and rachis, while those in the flag leaves were significantly increased by up to 20.87%, 49.40%, and 32.67%, respectively. DMSA application promoted the transport of HM from roots and lower stalks to flag leaves with a maximum increase of 34.55%, 52.65%, and 46.94%, respectively, whereas inhibited the transport of HM from flag leaves to panicle, rachis, and grains. Therefore, foliar application of DMSA reduced Cd, Pb, and As accumulation in rice grains by immobilizing HMs in flag leaves. Thus, this strategy could act as a promising agronomic measure for the remediation of mixed HM contamination in paddy fields.

Heavy metal pollution in paddy fields has caused widespread concerns due to the threat to food safety. The present study used low-cost sugarcane bagasse (SB) and two sugarcane bagasse materials modified with citric-acid (SSB) and citric-acid/Fe₃O₄ (MSB) to investigate their effects on the bioavailability of Cd in soil and Cd accumulations in rice in a pot experiment. The three organic amendments significantly decreased the Cd accumulation in plants by limiting its mobilization in soil. The MSB and SSB but not SB increased the soil pH and immobilized the Cd in soil significantly during the 120-day experiment. The amendments decreased Cd bioavailability through transforming to the stable fraction throughout the whole growth stage. The functional groups in the amendments (-OH, –COOH, C–O, -COO⁻ and Fe–O) and precipitates [Cd(NO₂)₂K(NO₂)₂, Cd(OH)₂ and Cd₇₅Zn₂₅Fe₂O₄] played active roles in Cd immobilization. Moreover, the three organic materials increased the content of Fe–Mn plaque on rice roots, which prevented its transport from soil to rice roots further. We also found that Fe competed with Cd for transporters and reduced potential Cd uptake and translocation in rice tissues. The addition of MSB and SB but not SSB inhibited the rice growth compared to the unamended control, indicating the potential of SSB in situ remediation. These results provide valuable information to use organic amendments for Cd passivation in soil and food safety.

Nano-silica as an important part of soil is an ideal carrier of passivator material. In this paper, nano-silica was modified by silane coupling agent containing mercapto group and iron (II) salt to afford an organic-inorganic hybrid containing –S-Fe-S functional group (coded as RNS-SFe) on the surface of nano-silica. Results demonstrate that the RNS-SFe nanoparticle has network-like spheroidal shape and a primary particle size is about 18.0 nm. The RNS-SFe hybrid as a potential immobilization agent for heavy metal in soil shows excellent performance for the remediation of the contaminated soil. Specifically, with a dosage of 3.0% (mass ratio) in the soil, it can immobilize bioavailable Pb, Cd, and As by 97.1%, 85.0%, and 80.1%, respectively. Namely, the RNS-SFe hybrid can transform the bioavailable Pb, Cd, and As into insoluble mercapto metal compounds (–S-Pb-S- and –S-Cd-S-) and less soluble iron arsenate (Fe₃(AsO₄)₂, FeAsO₄) precipitate on the surface of nano-silica particle, thereby reducing the toxicity and mobility of the toxic contaminant fractions. In the meantime, the immobilized products of the Pb, Cd and As fractions have good resistance against acid leaching. These results are contributive to the application of RNS-SFe for the remediation of multi-heavy metal-contaminated soils in field.

In situ immobilization of heavy metals in contaminated soils using industrial by-products is an attractive remediation technique. In this work, titanium gypsum (TG) was applied at two levels (TG-L: 0.15% and TG-H: 0.30%) to simultaneously reduce the uptake of cadmium (Cd), lead (Pb) and arsenic (As) in rice grown in heavy metal contaminated paddy soils. The results showed that the addition of TG significantly decreased the pH and dissolved organic carbon (DOC) in the bulk soil. TG addition significantly improved the rice plants growth and reduced the bioavailability of Cd, Pb and As. Particularly, bioavailable Cd, Pb and As decreased by 35.2%, 38.1% and 38.0% in TG-H treatment during the tillering stage, respectively. Moreover, TG application significantly reduced the accumulation of Cd, Pb and As in brown rice. Real-time PCR analysis demonstrated that the relative abundance of sulfate-reducing bacteria increased with the TG application, but not for the iron-reducing bacteria. In addition, 16S rRNA sequencing analysis revealed that the relative abundances of heavy metal-resistant bacteria such as Bacillus, Sulfuritalea, Clostridium, Sulfuricella, Geobacter, Nocardioides and Sulfuricurvum at the genus level significantly increased with the TG addition. In conclusion, the present study implied that TG is a potential and effective amendment to immobilize metal(loid)s in soil and thereby reduce the exposure risk of metal(loid)s associated with rice consumption.