Zeolite-supported nanoscale zero-valent iron (Z-NZVI) has great potential for metal(loid) removal, but its encapsulation mechanisms and ecological risks in real soil systems are not completely clear. We conducted long-term incubation experiments to gain new insights into the interactions between metal(loid)s (Cd, Pb, As) and Z-NZVI in naturally contaminated farmland soils, as well as the alteration of indigenous bacterial communities during soil remediation. With the pH-adjusting and adsorption capacities, 30 g kg⁻¹ Z-NZVI amendment significantly decreased the available metal(loid) concentrations by 10.2–96.8% and transformed them into strongly-bound fractions in acidic and alkaline soils after 180 d. An innovative magnetic separation of Z-NZVI from soils followed by XRD and XPS characterizations revealed that B-type ternary complexation, heterogeneous coprecipitation, and/or concurrent redox reactions of metal(loid)s, especially the formation of Cd₃(AsO₄)₂, PbFe₂(AsO₄)₂(OH)₂, and As⁰, occurred only under specific soil conditions. Sequencing of 16S rDNA using Illumina MiSeq platform indicated that temporary shifts in iron-resistant/sensitive, pH-sensitive, denitrifying, and metal-resistant bacteria after Z-NZVI addition were ultimately eliminated because soil characteristics drove the re-establishment of indigenous bacterial community. Meanwhile, Z-NZVI recovered the basic activities of bacterial DNA replication and denitrification functions in soils. These results confirm that Z-NZVI is promising for the long-term remediation of metal(loid)s contaminated farmland soil without significant ecotoxicity.

The Tharsis mine is presently abandoned, but the past intense exploitation has left large dumps and other sulphide-rich mining wastes in the area generating acid mine drainages (AMD). The main goal of this work is to study the effect of hydrogeochemical processes, hydrological regime and the waste typology on the physicochemical parameters and dissolved concentrations of pollutants in a deeply AMD-affected zone. Extreme leachates are produced in the area, reaching even negative pH and concentrations of up to 2.2 g/L of As and 194 g/L of Fe. The results of the comparison of ore grades of sulphide deposits with dissolved concentrations in waters shows that Pb is the least mobile element in dissolution probably due to the precipitation of Pb secondary minerals and/or its coprecipitation on Fe oxyhydroxysulphates. Arsenic, Cr, and V are also coprecipitated with Fe minerals. Seasonal patterns in metal contents were identified: elements coming from the host rocks, such as Al, Mn and Ni, show their maximum values in the dry period, when dilution with freshwater is lower and the interaction of water-rock processes and evaporation is higher. On the other hand, As, Cr, Fe, Pb and V show minimum concentrations in the dry period due to intense Fe oxyhydroxysulphate precipitation. In this sense, large sulphide rich waste heaps would be a temporal sink of these elements (i.e. Pb, As, Cr and V) in the dry period, and a significant source upon intense rainfalls.

The co-precipitation method was used to synthesize nano-magnetic adsorbent MnFe₂O₄ (nMFO), characterized through XRD, SEM, EDS, and BET techniques. The synthesized nMFO was used for hexavalent and trivalent chromium ions elimination from the aqueous phase. The optimum pH for the adsorption of Cr (VI) and Cr (III) was determined as 2 and 5, respectively. The chromium ions adsorption behavior was well interpreted through the pseudo-second order kinetics model. Furthermore, isotherm studies were conducted, and the obtained results indicated that Langmuir isotherm model could well justify the chromium ions adsorption process. Quick removal (less than 10 min) of both chromium ions and high removal efficiency were occurred using nMFO. The utmost adsorption capacity of trivalent and hexavalent chromium ions were determined as 39.6 and 34.84 mg g⁻¹, respectively. Thermodynamic studies on chromium adsorption revealed positive value for ΔH and negative value for ΔG, representing that chromium ions adsorption was an endothermic and spontaneous process. The multilinearity in the graphs of chromium ions adsorption was observed using intra-particle diffusion model. In this regard, the external mass transfer of chromium ions on synthesized nanoparticles was the important and controlling step in the adsorption process.

Hexavalent chromium and nitrate co-contaminated groundwater remediation are attracting extensive attention worldwide. However, the transformation pathways of chromium and nitrate and the interplay mechanism between them remain unclear. In this work, zeolite-supported nanoscale zero-valent iron/palladium (Z-Fe/Pd) was synthesized and used for the first time to simultaneously remediate Cr(VI) and nitrate. Transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy analyses confirmed that nanoscale zero-valent iron/palladium was successfully loaded onto zeolite and it exhibited good dispersibility and oxidation resistance. Results of batch experiments showed that the Cr(VI) and nitrate removal efficiencies decreased from 95.5% to 91.5% to 45% and 73%, respectively, with the initial solution pH increasing from 3.0 to 8.0. The removal rates and efficiencies of Cr(VI) and nitrate under anoxic conditions were higher than those under open atmosphere because the dissolved oxygen diminished the electron selectivity toward the target pollutants. Moreover, the presence of Cr(VI) inhibited nitrate reduction by forming Fe(III)-Cr(III) hydroxide to impede electron transfer. Cr(VI) removal was promoted by nitrate, within limits, by balancing the consumption and generation rate of Fe₃O₄, which enhanced electron migration from the Fe(0) core to the external surface. The removal capacities of Cr(VI) and nitrate reached 121 and 95.5 mg g⁻¹, respectively, which were superior to the removal capacities of similar materials. Results of product identification, XRD, and XPS analyses of spent Z-Fe/Pd indicated that the reduction of Cr(VI) was accompanied by adsorption and co-precipitation, whereas the reduction of nitrate was catalyzed by the synergism of Fe(0) and Pd(0). An alternative to the simultaneous remediation of Cr(VI) and nitrate from groundwater under anoxic conditions is provided.

Industrial by-products provide materials for remediation measures. In this study, a silicon-iron amendment was prepared from residue originating from acid-extracted copper (Cu) tailings based on thermal activation at temperatures ranging from 550 °C to 1150 °C for 30 min with the use of additives (CaO, Na₂CO₃, NaOH). The remediation performance of the amendment was evaluated through soil incubation and greenhouse pot experiments with vetiver (Vetiveria zizanioides). The results showed that the highest levels of soluble Si (6.11% of the total Si) and Fe (2.3% of the total Fe) in the amendment were achieved with thermal activation at 1150 °C for 30 min using an optimal ratio between residue and additives (residue: CaO: Na₂CO₃: NaOH = 1: 0.4: 0.4: 0.2). Heavy metal release indicated that the amendment could be safely used for soil remediation. The incubation experiments showed that the DTPA-extractable Cd, Cr and Pb in contaminated soils decreased with increasing amendment rate, which was not observed for As. The amendment-induced decrease in the Cd, Cr and Pb availability in contaminated soils could be explained by pH-change induced immobilization, Fe-induced chemisorption, Si-induced co-precipitation, and Ca-induced ion exchange. Correlation analysis suggested that there were significant negative correlations between DTPA-extractable Cd, Cr and Pb and the pH, Fe, Si, and Ca in soil pore water and soil. The most suitable amendment rate was determined to be 1% by balancing the efficacy and wise utilization of the amendment. The pot experiment demonstrated that the amendment promoted the vetiver growth and stimulated the accumulation of Cd and Cr in the roots. The amendment was proved to be promising for the phytostabilization of Cd, Cr and Pb in contaminated soils. Further investigations are required to determine whether the amendment is a tool for the long-term remediation of multi-metal-contaminated soils at the field scale.

Natural birnessite-like minerals are commonly enriched in various transitional metals (TMs), which greatly modify the mineral structure and properties. However few studies are yet conducted systematically on the effects of TM doping on birnessite reactivity towards Cr(III) oxidation. In the present study, the transformation behaviors of Cr(III) on Co-, Ni-, V-containing birnessites were investigated. Co and Ni doping generally decrease the mineral crystalline sizes and hydrodynamic sizes (DH) while V-doping greatly decreases the crystalline sizes but not the DH, owing to particle aggregation. Co and Ni firstly decrease and then increase the mineral zeta potentials (ζ) at pH4 while V decreases ζ. Electrochemical specific capacitances for Co-containing birnessites are gradually reduced, while those for Ni-doped birnessites are slightly reduced and for V-doped birnessites increased, which have a positively linear relationship with the amounts of Cr(III) oxidized by these samples. Cr(III) removal efficiencies from solution by these Co-, Ni- and V-containing birnessites are 26–51%, ∼62–72% and ∼96–100%, respectively, compared to ∼92% by pure birnessite. Cr(III) oxidation kinetics analysis demonstrates the gradual decrease of Mn(IV) and concurrent increase of Mn(III) and the adsorption of mainly Cr(III) on mineral surfaces. A negatively linear relationship exists between birnessite lateral sizes and the proportions of Mn(IV/III) consumed to oxidize Cr(III). Apparent initial Cr(III) oxidation rate (kobs) for Co-containing birnessites are greatly reduced, while those for Ni-doped samples moderately decreased and for V-doped samples first increased and then decreased. A positively or negatively linear relationship exists between kobs or the amount of Mn(II) released and the mineral Mn(IV) content respectively. Cr(III) oxidation probably initiates from layer edge sites of Ni-doped birnessites but the vacancies of Co- and V-containing birnessites. These results provide insights into the reaction mechanisms of Cr(III) with natural birnessite-like minerals.

Organic carbon (OC) can help control greenhouse gas emissions by participating in biogeochemical reactions and preventing the migration of contaminants in groundwater systems. The association of OC with Fe (Iron) oxide minerals plays a significant role in stabilizing OC and regulating the biogeochemical cycles of OC on the earth’s surface. Reclaiming farmland from lakes changes an original lake into a wetland, but the destiny of Fe bound-OC in the underlying aquitard during this process has been poorly understood. The mechanisms of migration and transformation of Fe bound-OC were investigated in subsurface aquitard sediments of three typical boreholes in the Chen Lake wetland, central China. The Fe bound-OC content in the natural sedimentary conditions (borehole A), transition area (borehole B), and intensive reclamation area (borehole C) were 0.17–3.87, 0.28–3.98 and 0.13–7.08 mg g⁻¹, respectively. The reclamation changed the redox, water, and infiltration conditions of the surface environment, resulting in a transformation of Fe oxides phases, and then cause the change of content and structure of Fe bound-OC. The fresh organic matter provided by undecomposed crops causes oxygen- and nitrogen-rich compounds to combine with Fe oxides extensively through adsorption, resulting in higher δ¹³C values of Fe bound-OC than non-Fe bound-OC. Fe bound-OC has strong resistance to biodegradation. The Fe bound-OC: total OC ratios generated by adsorption and coprecipitation on the surface layer (0 to −3.5 m) of borehole C was 10.37% and 18.86%, 6.92% and 12.46% higher than those of boreholes A and B, respectively. Coprecipitation has a stronger OC-binding ability and enriches more carboxylates and aromatics, while adsorption gradually assumed a dominant position in OC-Fe interaction in deep aquitard. The reduction dissolution of Fe oxide causes Fe bound-OC to transfer into pore water, leading to an increase of Fe ion and dissolved OC in deep strata.

Cadmium (Cd) is one of the most harmful and widespread environmental pollutants. Despite decades-long research efforts, the remediation of water contaminated by Cd has remained a significant challenge. A novel carbon material, pinecone biochar, was previously hypothesized to be a promising adsorbent for Cd, while so far, it has received little attention. This study evaluated the sorption capacity of pinecone biochar through isotherm experiments. Based on Langmuir model, the adsorption maximum for Cd(II) was up to 92.7 mg g⁻¹. The mechanism of Cd(II) adsorption on pinecone biochar was also explored through both thermodynamic and kinetics adsorption experiments, as well as both solution and solid-phase microstructure characterization. The solid-solution partitioning behaviour of Cd(II) fitted best with the Tόth model while the adsorption process followed a pseudo-second-order rate, suggesting that the Cd(II) adsorption on the pinecone biochar was mainly a chemisorption process. Microstructure characteristics and mechanism analysis further suggested that coprecipitation and surface complexation were the main mechanisms of Cd adsorption by biochar. Coprecipitation occurred mainly through the forms of Cd(OH)₂ and CdCO₃. Our results demonstrated that pinecone biochar was an efficient adsorbent which holds a huge potential for Cd(II) removal from aqueous solution.

Imidacloprid (IMI) is one of the most extensively used chlorinated organic pesticides and its widespread occurrence makes it attract increased public concern and scientific interest. Peroxymonosulfate (PMS) activation has been widely studied for the elimination of organic pollutants from water. But few studies are focused on their heterogeneous catalytic performance towards imidacloprid especially with the presence of silver ferrite nanoparticles (nAgFeO₂)-based catalysts. Herein, the catalyst, nAgFeO₂, was prepared via a co-precipitation method, and further applied to activate PMS for the removal of imidacloprid (IMI). Our results demonstrated that the prepared nAgFeO₂ significantly promoted the activation of PMS for removing IMI, and the removal of IMI followed a pseudo first-order kinetics model with the corresponding nAgFeO₂ dosage. Electron paramagnetic resonance (EPR) and quenching tests revealed the singlet oxygen (¹O₂)-mediated nonradical pathway, instead of hydroxyl radical (•OH) or sulfate radical (SO4•−), played the dominant role in the degradation of IMI. Eight products were identified and the degradation pathways of IMI were proposed. It is postulated that the primary site at the C-1 position of IMI was more easily attacked by the •OH yielding (6-chloropyridin-3-yl) methanol). While the site at the amidine nitrogen (2) of IMI was more likely attacked by the ¹O₂, and then reacted with •OH to produce 5-hydroxy imidacloprid. Overall, this study provides insights into the mechanisms of nonradical oxidation processes based on PMS for the elimination of pesticides from water, broadening the application of silver ferrite nanoparticles in wastewater treatment.

Ten sets of experiments with different settling times were conducted to investigate the effect of settling time on the adsorption of ¹³⁷Cs in seawater onto ammonium phosphomolybdate (AMP). The weight yields of AMP and ¹³⁷Cs yields in all groups were generally higher than 90%. The average weight yields of AMP in each group varied from 91.8 ± 0.5 to 95.9 ± 0.6% (1 SD), and the average ¹³⁷Cs yields in each group varied from 88.3 ± 3.0 to 97.8 ± 3.7% (1 SD). The results showed that equilibrium between Cs and AMP is established immediately after the addition of stable Cs carrier and AMP, implying that the solution could be filtered immediately after the coprecipitation forms. IAEA seawater proficiency test exercises also confirmed that the AMP precipitate does not need to be treated statically in the case of 2 g AMP and 3.7 mg Cs carrier in a seawater sample solution. The modified AMP preconcentration method simultaneously meets the requirements of routine and nuclear emergency monitoring of ¹³⁷Cs in seawater.