Iron-based materials have been widely investigated because of their high surface reactivity, which has shown potential for the remediation of metal(loid)s in groundwater. However, the disadvantages of structural stability and economic feasibility always limit their application in permeable reactive barrier (PRB) technology. In this study, zeolite-supported iron particles (Zeo-Fe) were synthesized by an innovative low-cost physical preparation method that is suitable for mass production. The removal efficiency and mechanism of typical metal(loid)s (Pb²⁺, Cd²⁺, Cr⁶⁺ and As³⁺) were subsequently investigated using various kinetic and equilibrium models and characterization methods. The results of scanning electron microscopy and energy dispersive spectrometry (SEM-EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) confirmed that zero valent iron (Fe⁰) and oxidation product (Fe₃O₄) were successfully loaded and efficiently dispersed on zeolite. The synthesized Zeo-Fe exhibited excellent adsorption and redox capacities for the cations Pb²⁺, Cd²⁺ and anions Cr⁶⁺, As³⁺. The increase in the pH resulting from Fe⁰ corrosion also enhanced the precipitation of Fe-metal(loid)s. The maximum removal capacity for Pb²⁺, Cd²⁺, Cr⁶⁺ and As³⁺ was up to 70.00, 9.12, 2.35 and 0.36 mg/g, respectively. The removal processes were well described by the pseudo-second-order kinetic model for Pb²⁺ and Cd²⁺, Lagergren pseudo first-order kinetics model for As³⁺ and double phase first order kinetics model l for Cr⁶⁺. Cr⁶⁺ was rapidly reduced to Cr³⁺ by the Fe⁰ stabilized on Zeo-Fe, and the oxidation of As³⁺ to As⁵⁺ was attributed to the Fe⁰/Fe²⁺ oxidation process at the interface over time, which was further demonstrated by the mineral phase and element valence analyses of reacted Zeo-Fe. The removal mechanism for metal(loid)s was a combination of physical and chemical processes, including adsorption, co-precipitation and reduction-oxidation. Conclusively, Zeo-Fe has been shown to have potential as an effective and economical material for removing various metal(loid)s used in PRB.

Development of efficient, green and low-cost natural mineral-based reductive materials is promising to remediation of hexavalent chromium(Cr(VI))-contaminated soil. Considering the synergetic effect between pyrite and zerovalent iron (ZVI), an activated pyrite supported ZVI(ZVI/FeS₂) with high reducing activity was developed by ball milling activation of natural pyrite and sulfidation of ZVI. The remediation property of ZVI/FeS₂ for Cr(VI)-contaminated soil was evaluated with different ZVI/FeS₂ dosage, soil-water ratio, initial pH, time and temperature, as well as the stability of Cr. The results showed that ZVI/FeS₂ possessed high reduction activity with soil Cr(VI) removal rate up to 99 % even under alkaline condition, and soil with different pH values eventually converged to neutral after 90 days, indicating that ZVI/FeS₂ has a good self-regulating alkaline ability. The reduction process conformed to Langmuir-Hinshelwood first-order kinetics and was a spontaneous and endothermic process. The lower activation energy of 17.97 kJ mol⁻¹ (usually 60–250 kJ mol⁻¹) indicated that the reduction reaction of Cr(VI) was particularly easy to occur. The speciation change of Cr in soil within 30 days demonstrated that the Cr in the soil was converted from a readily migratable state to a more stable state, where the Fe–Mn oxide bound fraction reached 85.03 % due to the generation of Cr(III)/Fe(III) co-precipitation. The results of long-term stability experiments showed that the leaching concentrations of Cr(VI) and total Cr decreased significantly after the ZVI/FeS₂ treatment and remained stable at very low levels for 180 days. This study provided a sustainable way to fully utilize natural pyrite minerals to obtain iron-bearing reductive materials for feasible, effective and long-term stable immobilization of Cr(VI) in soil.

Phosphogypsum (PG) is disposed worldwide in large stacks usually placed in coastal zones, as in the case of Huelva (SW of Spain), where around 100 Mt of PG are stored on the salt marshes of the Tinto River estuary covering a surface of about 1000 ha. This management generates the weathering of PG, and due to its high acidity (pH ≈ 2) and pollutant load can provoke significant emissions into their surroundings. In this work were evaluated by laboratory experiments the effects of pH increase in the behaviour of heavy metals and natural radionuclides during the mixing of phosphogypsum leachates with seawater.The acidic phosphogypsum leachates showed concentrations of heavy metals from two to three orders of magnitude higher than natural continental waters, and natural radionuclides (U-isotopes and ²¹⁰Po) from four to five orders of magnitude higher than unperturbed aquatic systems. Major elements and some heavy metals as Mn, Ni, Cd, As, Sb and Co showed a conservative behaviour during the neutralisation of the leachates with seawater, remaining in the liquid phase, while other ones as Al, Fe, Cr, Zn, Cu, Pb precipitated and/or were adsorbed onto the solid phase. The U-isotopes and ²¹⁰Po showed a clear non-conservative behaviour probably due to coprecipitation/adsorption processes onto the formed precipitates, but while ²¹⁰Po reached a total removal at pH ≈ 7, U- isotopes after a total removal at pH ≈ 5 returned into the liquid phase due to redissolution/desorption processes at near neutral pH.The formed precipitates, mainly composed by iron phosphates particles, showed heavy metal and natural radionuclide concentrations from one to three orders of magnitude higher than unperturbed soils. All these facts demonstrate the serious environmental impact produced by the PG stacks into their surroundings and the urgency of effective restoration measures.

High-arsenic wastewater derived from the metallurgical industry of nonferrous minerals is one of the most dangerous arsenic (As) sources that usually follow the emission of massive hazardous arsenic-bearing wastes. Considering the properties of red mud (RM), we propose an alternative and environmentally friendly method for the efficient remediation of high-arsenic wastewater using RM through formation of AlAsO₄@silicate precipitate, aiming at ''zero-emission of hazardous solid waste''. The results show nearly 100% of arsenic could be stepwisely removed from high-arsenic wastewater and reduce the arsenic concentration from 6100 mg/L to 40 μg/L using RM at room temperature. The highest arsenic removal capacity of RM reaches 101.5 mg/g at a RM-to-wastewater ratio of 40 g/L due to the superior arsenic adsorption and the co-precipitation of arsenate and Al³⁺ to form insoluble aluminum arsenate. The silicate shell of arsenic-loaded RM created at an alkaline condition acts as an arsenic stabilizer, resulting in a leached arsenic concentration of 1.2 mg/L in TCLP tests. RM acts as a highly effective arsenic remover and stabilizer for the disposal of high-arsenic wastewater. It shows great potential for the remediation of wastewater containing heavy metals with varying concentrations to produce clean water available for industrial purpose.

Selenium (Se) and arsenic (As) are toxic contaminants in surface water and drinking water. The human body needs little quantity of Se, but too high dose is not allowed. Metal oxides such as iron oxides were used for adsorption or co-precipitation removal of As from water. However, the regeneration and stability problems of metals oxides sorbents are unsatisfactory , and there is not enough adsorbent for Se removal from water also. We developed the acrylic amine fiber (AAF) for adsorption reomval of Se and As from water and systematically studied the influenced factors. Batch experiments were conducted for investigating the adsorption edges, while column filtration tests were employed for dynamic application edges. At neutral pH, the Langmuir isotherm fittings gave the maximum adsorption capacities of As(V), As(III), Se(VI) and Se(IV) are 270.3, 40.5, 256.4, and 158.7 mg/g, respectively. Effects of co-existing inorganic anions on As(V) and Se(VI) adsorption using AAF gave the order of PO₄³⁻ > SO₄²⁻ > NO₃⁻ > SiO₃²⁻, while different organic acids obey the order of citric acid > oxalic acid > formic acid. Fourier transform infrared analysis showed the PO₄³⁻ and SO₄²⁻ competition mechanisms are electrostatic repulsions, while the competition of organic acids derived from acid-base reaction between the carboxyl group and the amino group. Column filtration and regeneration results showed that the spent AAF can be regenerated using 0.5 mol/L HCl solution and reused with no much decrease of adsorption capacity.

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.

In May 2017, a spill from La Zarza pit lake (SW Spain) resulted in the release of approximately 270,000 m3 of extremely acidic waters to the Odiel River. Around 780 × 103 kg of Fe, 170 × 103 kg of Al, 2.15 × 103 kg of As and high amounts of other trace metals and metalloids were spilled. The purpose of this study is to explain the causes, consequences and impacts of the mine spill on the receiving water bodies. To this end, an extensive sampling along the mine site, river and estuary as well as a hydrological model of the pit lake was performed. Around 53 km of the Odiel River's main course, which was already contaminated by acid mine drainage (AMD), were affected. The mine spill resulted in an incremental impact on the Odiel River water quality. Thus, dissolved concentrations of some elements increased in the river up to 450 times; e.g. 435 mg/L of Fe and 0.41 mg/L of As. Due to low pH values (around 2.5), most metals (e.g., Cu, Zn, Mn, Cd) were transported in the dissolved phase to the estuary, exhibiting a conservative behavior and decreasing their concentration only due to dilution. However, dissolved concentrations of Fe, Cr, Pb, Se, Sb, Ti, V and especially As decreased significantly along the river due to Fe precipitation and sorption/coprecipitation processes. At the upper zone of the estuary, a noticeable increment of metal concentrations (up to 77 times) was also recorded. The water balance illustrates the existence of groundwater inputs (at least 16% of total) to the pit lake, due probably to local infiltration of rainwater at the mining zone. The probable existence of an ancient adit connected to the pit lake indicates that potential releases could occur again if adequate prevention measures are not adopted.

This study aimed to develop a novel in-situ method to directly remove toxic hexavalent chromium anions from groundwater. The characteristics of Mg/Al-layered double hydroxides (LDH) involving in-situ synthesis and interlayer exchangeable anions can facilitate to remove Cr(VI) from solution. Two different methods of LDH preparation were employed to explore the adsorption efficiency of (di)chromates, such as traditional coprecipitation (CO₃-LDH) and innovative in-situ synthesis (in-situ-LDH). The synthesized LDH samples were characterized using scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and zeta potential. The results demonstrated that the adsorptive amount of Cr(VI) for the in-situ synthesis process dramatically increased with an increase in initial Cr(VI) concentrations from 100 mg/L to 900 mg/L. The kinetic study indicated that the constant rate (k₂) of the pseudo-second-order equation significantly decreased when the initial concentration of Cr(VI) exceeded 500 mg/L. The removal efficiency of Cr(VI) was slightly dependent on solution pH (5.0–12) values. The in-situ-LDH absorbent (339 mg/g) exhibited the significantly higher Langmuir maximum adsorption capacity than CO₃-LDH (246 mg/g). The primary adsorption mechanism was anion exchange; meanwhile, the adsorption-coupled reduction mechanism also played an integral role. The advanced in-situ synthetic method can be developed to efficiently remove toxic hexavalent chromium anions from groundwater.

The main objectives of this study were to evaluate global uncertainty in the prediction of Distribution coefficients (Kds) for several Trace Metals (TM) (Cd, Cu, Pb, Zn) through the probabilistic use of a geochemical speciation model, and to conduct sensitivity analysis in speciation modeling in order to identify the main sources of uncertainty in Kd prediction. As a case study, data from the Loire river (France) were considered. The geochemical speciation model takes into account complexation of TM with inorganic ligands, sorption of TM with hydrous ferric oxides, complexation of TM with dissolved and particulate organic matter (i.e. dissolved and particulate humic acids and fulvic acids) and sorption and/or co-precipitation of TM to carbonates. Probability Density Functions (PDFs) were derived for physico-chemical conditions of the Loire river from a comprehensive collection of monitoring data. PDFs for model parameters were derived from literature review. Once all the parameters were assigned PDFs that describe natural variability and/or knowledge uncertainty, a stepwise structured sensitivity analysis (SA) was performed, by starting from computationally ‘inexpensive’ Morris method to most costly variance-based EFAST method. The most sensitive parameters on Kd predictions were thus ranked and their contribution to Kd variance was quantified. Uncertainty analysis was finally performed, allowing quantifying Kd ranges that can be expected when considering all the sensitive parameters together.