In this study, we firstly used alginate to enhance an electrokinetic technology to remediate soil contaminated with divalent heavy metals (Pb²⁺, Cu²⁺, Zn²⁺). The mechanisms of alginate-associated migration of metal ions in electric field were confirmed. Alginate resulted in a high electrical current during electrokinetic process, and soil conductivity also increased after remediation. Obvious changes in both electroosmotic flow and soil pH were observed. Moreover, these factors were affected by increasing alginate dosage. The highest Cu (95.82%) and Zn (97.33%) removal efficiencies were obtained by introducing 1 wt% alginate. Alginate can desorb Cu²⁺ and Zn²⁺ ions from soil by forming unstable gels, which could be dissociated through electrolysis. However, Pb²⁺ ions did not easily migrate out of the contaminated soil. The density functional theory (DFT) calculations show Pb²⁺ ions could form a more stable coordination sphere in metal complexes than Cu²⁺ and Zn²⁺ ions. The metal removal efficiency was decreased by increasing alginate dosage at a high level. More alginate could provide more carboxyl ligands for divalent metal ions to stabilize gels, which were difficult to dissociate by electrolysis. In summary, the results indicate it is potential for introducing alginate into an electrokinetic system to remediate Cu- and Zn- contaminated soil.

In this study, a novel approach was employed for the remediation of cationic and anionic metals/metalloids co-contaminated soil by tetrapolyphosphate enhanced soil washing coupled with ferrous sulfide treatment. Tetrapolyphosphate could simultaneously enhance the desorption of cationic metals (Pb and Zn) and anionic metal/metalloid (Cr and As) from the contaminated soil in the whole tested pH range of 2–10. With addition of 0.15 mol/L tetrapolyphosphate at pH 7.0, the removal ratio of Pb, Zn, As and Cr could achieve 83.1%, 70.4%, 75.7% and 66.4% respectively. The fractionation analysis of heavy metals/metalloids demonstrated the release of exchangeable and Fe/Mn bound forms contributed to most desorption of Pb and Zn. The decreases of non-specifically sorbed form and amorphous and poorly-crystalline hydrous oxides of Fe and Al bound form were responsible for most removal of As. The comparison with other common washing agents (EDTA, oxalate and phosphate) under their respective optimal dosage could confirm that tetrapolyphosphate was superior to simultaneously desorb the cationic and anionic metals/metalloids with higher efficiency. After 12 h, applying 150 mg/L FeS at pH 3.5 could totally remove Pb, Zn, As and Cr from the washing effluent by sulfide precipitation, reduction and adsorption processes. Higher pH would inhibit the removal of As and Cr by FeS. Meanwhile, the residual of tetrapolyphosphate could be totally recovered from the washing effluent by employing anion exchange resin. This study suggests tetrapolyphosphate enhanced soil washing coupled with ferrous sulfide treatment is a promising approach for remediation of cationic and anionic metals/metalloids co-contaminated soil in view of its high efficiency and simple operation.

Identifying the bioavailability and release-desorption mechanism of heavy metals (HMs) in soil is critical to understand the release risk of HMs. Simultaneously, the mechanistic investigation of affecting the bioavailability of HMs in soil is necessary, such as the grain-size distribution and soil mineralogy. Herein, the bioavailability of HMs (Cu, Cd, Ni, Pb, and Zn) in different area soils near a typical copper-smelter was evaluated by the sequential extraction technique (BCR), diffusive gradients in thin-films (DGT), and DGT-induced fluxes in sediments (DIFS) model. Results showed that the HMs proportion of the residual fraction in all soils was the highest. The average bioavailability concentration (CDGT) of Cu and Cd in industrial soil was the highest, with 45.12 μg· L⁻¹ and 9.06 μg· L⁻¹. The result of DIFS model revealed that the decreased order of the mean value of desorption rate constant (K₋₁) was Cd > Zn > Ni > Cu > Pb, 5.91 × 10⁻⁵, 4.96 × 10⁻⁵, 2.89 × 10⁻⁵, 9.64 × 10⁻⁶, and 8.69 × 10⁻⁶, respectively. According to the spatial distribution of release potential (R-value), the release potential of labile-Cu in agricultural soil was the highest, which was mainly attributed to fertilizer application in farmland. Simultaneously, the reduced hydroxyl was also related to the agricultural activities, resulting in the weakened adsorption capacity of HMs by soil. Redundancy analysis (RDA) results showed that the bioavailability of Cd, Ni, and Zn was mainly driven by soil pH, while the bioavailability of Cu and Pb was primarily driven by dissolved organic carbon (DOC). Meanwhile, carbonate minerals had a positive correlation with the bioavailability of Cd, Ni, and Zn, which could promote the release of HMs in mining soil as chemical weathering progresses. In conclusion, this study provides a structured method which can be used as a standard approach for similar scenarios to determine the geochemical fractionation, bioavailability, and release kinetics of heavy metals in soils.

The effectiveness and feasibility of the three biochar materials for remediation of arsenic (As) and lead (Pb) contaminated soil were explored in this study. Significant reduction of bioaccessibility and migration risks of both heavy metals have been explained mechanistically by incubation, column experiments and numerical simulation. Langmuir equation fitted As and Pb sorption isotherms better in the control and biochar (BC) amended soils, while Freundlich model was more suitable for iron modified biochar (Fe-BC) and sulfur/iron modified biochar (S/Fe-BC) amended soils, indicating that modified biochar promoted chemical adsorption process for As and Pb. For the three biochar materials, S/Fe-BC showed the best effects on reducing the bioavailability of As and Pb, with a decrease of 40.42%–64.21%. The reduction in bioaccessibility by metal portioning into available and non-available fractions was better for illustrating the mechanisms including adsorption, precipitation/coprecipitation and As(III) oxidation behind S/Fe-BC efficacy. Moreover, S/Fe-BC can effectively inhibit the leaching behavior of As and Pb under acid rain, which increased by 99.89% and 90.18%, respectively, compared with the control. The HYDRUS-1D modeling indicated that S/Fe-BC could continuously treat As (100 mg/L) and Pb (1000 mg/L) contaminated water for 16.22 years and 40.86 years, respectively, and ensure the groundwater quality criteria being met. Based on these insights, we believe that our study will provide meaningful information about the potentials of biochar derived materials for soil heavy metals’ remediation.

Lead (Pb) is a toxic metal in industrial production, which can seriously threat to human health and food safety. Thus, it is particularly crucial to reduce the content of Pb in the environment. In this study, raw fly ash (FA) was used to synthesise a new active silicate materials (IM) employing the low-temperature-assisted alkali (NaOH) roasting approach. The IM was further synthesised to form zeolite-A (ZA) using the hydrothermal method. The physicochemical characteristics of IM and ZA amendments before and after Pb²⁺ adsorption were analysed using the Scanning electron microscope-Energy Dispersive Spectrometer (SEM-EDS), Fourier Transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) apparatuses. The results revealed the considerably change in the microstructure and functional groups of IM and ZA amendments, conducive to Pb²⁺ removal. Moreover, a 3-year field experiment revealed that the IM and ZA significantly improved the growth of rice and reduced available Pb by 21%–26.8% and 9.7%–16.9%, respectively. After 3 years of remediation, the Pb concentration of the rice grain reached the national edible standard (≤0.2 mg kg⁻¹) of 0.171 mg kg⁻¹ and 0.179 mg kg⁻¹, respectively. Meanwhile, the concentration of acid-exchangeable Pb reduced, while those of reducible and residual fractions of Pb increased. There was no significant difference between the IM and ZA treatments. The potential mechanisms of remediation by the amendments were ion-exchange, complexation, precipitation, and electrostatic attraction. Overall, the results indicate that IM is suitable for the remediation of contaminated soil and promotes safe food production, and develops an environmentally friendly and cost-effective amendment for the remediation of polluted soil.

Combined chemical oxidation and bioremediation is a promising method of treating polycyclic aromatic hydrocarbon (PAH) contaminated soil, wherein indigenous soil bacteria play a critical role in the subsequent biodegradation of PAHs after the depletion of the oxidant. In this study, different Fenton conditions were applied by varying either the oxidation mode (conventional Fenton (CF), Fenton-like (LF), modified Fenton (MF), and graded modified Fenton (GMF)) or the H₂O₂ dosage (0%, 3%, 6%, and 10% (v/v)) to treat PAH contaminated soil. The results revealed that when equal dosages of H₂O₂ are applied, PAHs are significantly removed following oxidation treatment, and the removal percentages obeyed the following sequence: CF > GMF > MF > LF. In addition, higher dosages of H₂O₂ improved the PAH removal from soil treated with the same oxidation mode. The ranges of total PAHs removal efficiencies in the soil added 3%, 6%, and 10% of H₂O₂ (v/v) were 18.04%∼59.48%, 31.88%∼71.83%, and 47.56%∼78.16%, respectively. The PAH removal efficiency decreased with increasing ring numbers for the same oxidation treatment. However, the negative influences on soil bacterial abundance, community composition, and function were observed after Fenton treatment. After Fenton oxidation, the bacterial abundance in the soil received 3%, 6%, and 10% of H₂O₂ (v/v) decreased 1.96–2.69, 2.44–3.22, and 3.09–3.42 orders of magnitude compared to the untreated soil. The soil bacterial abundance tended to be impacted by the oxidation mode and H₂O₂ dosage simultaneously. While the main factor influencing the soil bacterial community composition was the H₂O₂ dosages. The results of this study showed that different oxidation mode and H₂O₂ dosage exhibited different effects on PAHs removal and soil bacteria (including abundance, community composition, and function), and there was a trade-off between the removal of PAHs and the adverse impact on soil bacteria.

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.

Though many studies pertaining to soil bioremediation have been performed to study the microbial kinetics in shake flasks, the process efficiency in column tests is seldom. In the present study, soil columns tests were carried out to study the biodegradation of soil contaminated with a high concentration of diesel (≈19.5 g/kg) petroleum hydrocarbons expressed as C₁₀–C₅₀. Experiments were done with crude enzymatic cocktail produced by the hydrocarbonoclastic bacterium, Alcanivorax borkumensis. A. borkumensis was grown on a media with 3% (v/v) motor oil as the sole carbon and energy source. The effects of the enzyme concentration, treatment time and oxidant on the bioremediation efficiency of C₁₀–C₅₀ were investigated. A batch test was also carried out in parallel to investigate the stability of the enzymes and the effect of the biosurfactants on the desorption and the bioconversion of C₁₀–C₅₀. Batch tests indicated that the biosurfactants significantly affected the desorption and alkane hydroxylase and lipase enzymes, maintained their catalytic activity during the 20-day test, with a half-life of 7.44 days and 8.84 days, respectively. The crude enzyme cocktail, with 40 U/mL of lipase and 10 U/mL of alkane hydroxylase, showed the highest conversion of 57.36% after 12 weeks of treatment with a degradation rate of 0.0218 day⁻¹. The results show that the soil column tests can be used to optimize operating conditions for hydrocarbon degradation and to assess the performance of the overall bioremediation process.