Solidification/stabilization technology is one of the most desirable technologies for the remediation of heavy metal contaminated soils due to its convenience and effectiveness. The annual production of alkaline industrial wastes in China is in the hundreds of millions of tons. Alkaline industrial wastes have the potential to replace conventional stabilizers because of their cost effectiveness and performance in stabilizing heavy metals in soils. This paper systematically summarizes the use of four alkaline industrial wastes (soda residue, steel slag, carbide slag, and red mud) for the solidification/stabilization of heavy metal contaminated soils and provides a comprehensive analysis of the three mechanisms of action (hydration, precipitation, and adsorption) and factors that influence the process. In addition, the environmental risks associated with the use of alkaline industrial wastes are highlighted. We found that soda residues, steel slag and carbide slag are appropriate for solidification/stabilization of Pb, Cd, Zn and Cu, while red mud is a potential passivation agent for the stabilization of As in soils. However, implementation of remediation methods using alkaline industrial wastes has been limited because the long-term effectiveness, synergistic effects, and usage in soils containing multiple heavy metals have not been thoroughly studied. This review provides the latest knowledge on the mechanisms, risks, and challenges of using alkaline industrial wastes for solidification/stabilization of heavy metal contaminated soils.

Soil contaminated with toxic heavy metals (THMs) was stabilized by adding a combination of waste resources in 7.0 wt%, including coal-mine drainage sludge, waste cow bone, and steelmaking slag, in the ratio of 5:35:60. Subsequently, corn and peanut were cultivated in treated soil to investigate the effects of the waste resources on THM mobility in soil and translocation to plants. Sequential extraction procedures (SEP) was used to analyze mobile phase THMs which could be accumulated in the plants. SEP shows that mobile Pb, Cd, Cu, Zn, Ni, Cr, and As were reduced by 8.48%, 29.22%, 18.85%, 21.66%, 4.58%, 62.78%, and 20.01%, respectively. The bioaccumulation of THMs was clearly hindered by stabilization; however, the increment in the amount of immobile-phase THMs and change in the amount of translocated THMs was not proportional. The corn grains grown above the soil surface were compared with the peanut grains grown beneath the soil surface, and the results indicating that the efficiency of stabilization on THM translocation may not depend on the contact of grain to soil but the nature of plant. Interestingly, the results of bioaccumulation with and without stabilization showed that the movement of some THMs inside the plants was affected by stabilization.

The release of hexavalent chromium [Cr(VI)] into water bodies poses a major threat to the environment and human health. However, studies of the biological response to Cr(VI) are limited. In this study, a toxic bacterial mechanism of Cr(VI) was investigated using Pannonibacter phragmitetus BB (hereafter BB), which was isolated from chromate slag. The maximum Cr(VI) concentrations with respect to the resistance and reduction by BB are 4000 mg L−1 and 2500 mg L−1, respectively. In the BB genome, more genes responsible for Cr(VI) resistance and reduction are observed compared with other P. phragmitetus strains. A total of 361 proteins were upregulated to respond to Cr(VI) exposure, including enzymes for Cr(VI) uptake, intracellular reduction, ROS detoxification, DNA repair, and Cr(VI) efflux and proteins associated with novel mechanisms involving extracellular reduction mediated by electron transfer, quorum sensing, and chemotaxis. Based on metabolomic analysis, 174 metabolites were identified. Most of the upregulated metabolites are involved in amino acid, glucose, lipid, and energy metabolisms. The results show that Cr(VI) induces metabolite production, while metabolites promote Cr(VI) reduction. Overall, multi-enzyme expression and metabolite production by BB contribute to its high ability to resist/reduce Cr(VI). This study provides details supporting the theory of Cr(VI) reduction and a theoretical basis for the efficient bioremoval of Cr(VI) from the environment.

The use of Ni and Cu isotopes for tracing contamination sources in the environment remains a challenging task due to the limited information about the influence of various biogeochemical processes influencing stable isotope fractionation. This work focuses on a relatively simple system in north-east Norway with two possible endmembers (smelter-bedrock) and various environmental samples (snow, soil, lichens, PM10). In general, the whole area is enriched in heavy Ni and Cu isotopes highlighting the impact of the smelting activity. However, the environmental samples exhibit a large range of δ⁶⁰Ni (−0.01 ± 0.03‰ to 1.71 ± 0.02‰) and δ⁶⁵Cu (−0.06 ± 0.06‰ to −3.94 ± 0.3‰) values which exceeds the range of δ⁶⁰Ni and δ⁶⁵Cu values determined in the smelter, i.e. in feeding material and slag (δ⁶⁰Ni from 0.56 ± 0.06‰ to 1.00 ± 0.06‰ and δ⁶⁵Cu from −1.67 ± 0.04‰ to −1.68 ± 0.15‰). The shift toward heavier Ni and Cu δ values was the most significant in organic rich topsoil samples in the case of Ni (δ⁶⁰Ni up to 1.71 ± 0.02‰) and in lichens and snow in the case of Cu (δ⁶⁵Cu up to −0.06 ± 0.06‰ and −0.24 ± 0.04‰, respectively). These data suggest an important biological and biochemical fractionation (microorganisms and/or metal uptake by higher plants, organo-complexation etc.) of Ni and Cu isotopes, which should be quantified separately for each process and taken into account when using the stable isotopes for tracing contamination in the environment.

Metal immobilization may contribute to the environmental management strategy of dredged sediment landfill sites contaminated by metals. In a field experiment, amendment effects and efficiency were investigated, focusing on plants, springtails and bacteria colonisation, metal extractability and sediment ecotoxicity. Conversely to hydroxylapatite (HA, 3% DW), the addition of Thomas Basic Slag (TBS, 5% DW) to a 5-yr deposited sediment contaminated with Zn, Cd, Cu, Pb and As resulted in a decrease in the 0.01 M Ca(NO₃)₂-extractable concentrations of Cd and Zn. Shoot Cd and Zn concentration in Calamagrostis epigejos, the dominant plant species, also decreased in the presence of TBS. The addition of TBS and HA reduced sediment ecotoxicity and improved the growth of the total bacterial population. Hydroxylapatite improved plant species richness and diversity and decreased antioxidant enzymes in C. Epigejos and Urtica dïoica. Collembolan communities did not differ in abundance and diversity between the different treatments.

Lead-zinc slag (LZS) is a solid waste product that is rich in silicon and aluminum and has enormous resource potential for functional environmental functional geopolymer materials. Unfortunately, the solidification mechanism of heavy metals in geopolymers is still unclear, which is detrimental to the heavy metal solidification of LZS. In this study, we comprehensively studied and demonstrated the solidification mechanisms of Pb and Zn in geopolymers, based on the preparation of high-performance LZS-based geopolymers (compressive strength up to 89.3 MPa, and Pb and Zn solidification efficiency up to 93.1% and 90.0%, respectively). Thereafter, the solidification mechanism differences between Pb and Zn were explained by electronegativity and ion potential. Due to the ionic potential order of Zn²⁺> Pb²⁺> Na⁺, both Zn²⁺ and Pb²⁺ could exchange with Na⁺ in the geopolymer. In addition, due to the electronegativity order of Pb > Si > Zn, Pb could attack the [SiO₄] structure and form covalent bonds in the Pb–O structure, while Zn did not (shown by Raman spectroscopy). As a result, Pb simultaneously solidified in the geopolymer through covalent bonding and ion exchange, while Zn was solidified mainly by ion exchange. Thus, this work provides new perspectives and ideas for the solidification mechanisms of heavy metals in geopolymers.

In this study, municipal solid waste incineration fly ash (MSWIFA) was first washed (pretreatment) with pure water with liquid to solid (L/S) ratio of 2, 3, 6, 10, to understand the removal efficiency of chlorine and sulphate, as well as its consequent ability as alkaline activator for granulated blast furnace slag (GGBFS). Washed MSWIFA was blended with GGBFS at a fixed ratio of 3:7 to examine their impact on mechanical properties, reaction mechanism, microstructure and leaching behavior. The results showed that chlorine in MSWIFA (>70%) can be washed out easily, while the removal of sulphate was largely depended on the L/S. GGBFS can be better activated by a low L/S (e.g. 2) washed-MSWIFA with attaining the compressive strength of 45.2MPa at 28 days. The higher chlorine and sulphate contents retained in the washed-MSWIFA, the higher the total heat release in the activated GGBFS system. Calcium silicate hydrate (C–S–H), ettringite (AFt) and Friedel’s salt were the main hydration products of the activated binders. The rapid formation of AFt was mainly responsible for the 1-day strength development. Large amounts of Friedel’s salts were formed from 1 day to 3 days associated to the inhibition of sulphate, and the presence of C–S–H played the key role in long-term strength development. The leaching test of heavy metals and soluble ions also demonstrated that washed MSWIFA activated GGBFS binders were harmless to the environment.

Different prediction models have important effects on the accuracy of spatial distribution simulations of heavy metals in soil. This study proposes a model (RFOK) combining a random forest (RF) with ordinary kriging (OK), multi-source environmental data such as terrain elements, site environmental elements, and remote sensing data were incorporated to predict the spatial distribution of heavy arsenic (As) in soil of a certain large arsenic slag site. The predictions results of RFOK were compared with those obtained using the RF, OK, inverse distance weighted (IDW), and stepwise regression (STEPREG) models for assessment of prediction accuracy. The results showed that arsenic pollution was widely distributed and the center of the site, including arsenic slag stacking area and production area were seriously polluted. The overall spatial distribution of arsenic pollution simulated by the five models was similar, but the IDW, RF, OK, and STEPREG showed less spatial variation of soil pollution, while RFOK simulation can better express the characteristics of details in change. The cross-validation results showed that RFOK had the lowest root-mean-square error (RMSE), mean absolute error (MAE), and mean relative error (MRE) relative to the other four models, followed by RF, OK, IDW, and STEPREG. The RMSE, MAE and MRE of RFOK decreased by 62.2%, 64.3% and 68.7%, respectively, relative to the RF model with the second highest accuracy. Compared with the traditional spatial distribution prediction model, the RFOK model proposed in this study has excellent spatial distribution prediction ability for soil heavy metal pollution with large spatial variation characteristics, which can fully explain the nonlinear relationship between pollutant content and its environmental impact elements.

In-site remediation is a relatively promising and socially acceptable technique for heavy metal contaminated soils. But the key task is to select cost-effective and environment-friendly amendents for the consideration of practical application. Based on the property of four typical silicate wastes such as straw ash (SA), coal fly ash (CFA), ferronickel slag (FNS) and blast-furnace slag (BFS), effects of four wastes on available Cd content and Cd chemical speciation in amended soils, and physicochemical properties of the amended soils were carried out in the study. The results showed that four wastes were dominately composed of the amorphous phases with OH⁻ ions readily released. When the weight ratio of silicate wastes to artificial Cd-contaminated soils reached 10%, the available Cd contents decreased from 4.12 mg/kg in untreated soils to 1.94, 1.92, 1.45 and 1.53 mg/kg in amended soils by adding SA, CFA, FNS and BFS respectively, after the soils were amended for 30 days. The residual fraction of Cd (R) was 2.54, 2.48, 2.77 and 2.58 times higher in amended soil than that in untreated soil when SA, CFA, FNS and BFS was added, respentively. The soil pH and CEC were improved. The amended soils by adding SA and FNS were looser than those by adding CFA and BFS, and air permeability of the amended soils by SA was better than that by FNS.

Particulate organic matter (POM) significantly affects the distribution of heavy metals in contaminated soil. However, the effect of POM on the fate of heavy metals during in situ-aided phytostabilization of waste slag is unclear. The objective of this study was to investigate the distributions of heavy metals such as Cu, Pb, Zn, and Cd in the POM fractions at a zinc smelting waste slag site under in situ-aided phytostabilization after five years. The results showed that the litters and residues of four plants―Arundo donax, Broussonetia papyrifera, Cryptomeria fortunei, and Robinia pseudoacacia―decomposed to form different POM size fractions. The percentage of the 0.05–0.25 mm POM size fraction was the highest, followed by the >1 mm and 0.5–1 mm POM size fractions, and that of the 0.25–0.5 mm POM size fraction was the lowest. The masses of POM derived from the four plants were in the following order: C. fortunei > B. papyrifera > A. donax > R. pseudoacacia. The contents, enrichment coefficients, and mass loads of heavy metals such as Cu, Pb, Zn, and Cd in the POM increased with decreasing POM size, and those in the 0.05–0.25 mm POM size fraction were the highest. The mass load of heavy metals in the POM occurred in the following order: Cu > Cd > Zn > Pb. The surfaces of the POM with coarser and smaller size fractions were smoother and rougher, respectively, and the smaller POM size fractions had larger specific surface areas. The main functional groups in the different POM size fractions were –COOH, –OH, CO, CC, C–H, Si–O, and –CH₃. The POM fractions played a significant role in determining the distribution of heavy metals in the revegetated waste slag. These findings have important implications for aided phytostabilization, which significantly influences the fate and speciation of heavy metals at the phytoremediation site.