Precipitation Of Oxides Research Articles

Recovery of critical and strategic metals from scrap marble-cutting tools by oxidative leaching and precipitation

Scrap marble-cutting tool segments (SMCTSs) generated within marble-cutting applications can be regarded as an important secondary resource owing to their high content of base/precious/critical metals (i.e. Co, Cu and Ag) as well as synthetic diamonds. In this study, sulphuric acid-hydrogen peroxide leaching of copper cobalt and silver from SMCTSs was studied using the central composite design for experiments. Extractions of cobalt (≥73.8 %) and iron (≥86.6 %) were more extensive than copper (≤78.3 %) and silver (≤35.1 %), linked with their relative nobilities. Data analysis has confirmed that increasing the acid concentration or temperature enhances the leaching of metals. Copper and silver leaching improves with H2O2 concentration, while high cobalt and iron leaching can be readily achieved without H2O2. Silver was selectively precipitated (98.9 %) as AgCl with 8.8 % Cu and 0.7 % Co losses from the leach solution. Copper and cobalt were also recovered selectively by increasing the pH to 5.5 and 8.5 respectively after the removal of iron at pH 3.5. These findings have revealed that cobalt, copper, and silver could be selectively recovered by the proposed leaching and precipitation approaches from SMCTSs.

Efficient separation and recovery of Co and Ni from ammonium sulfate roasting‐water leaching solutions of oceanic cobalt‐rich crusts by sulfide precipitation and P507–Cyanex 272 synergistic extraction

AbstractOceanic cobalt‐rich crusts contain many valuable metals including Co, Ni, Cu, and Mn, of which Co and Ni are scarce metal resources on terrestrial land. Co, Ni, Cu, and Mn in cobalt‐rich crusts can be efficiently extracted by the ammonium sulfate roasting‐water leaching (ARWL) process, but separating and recovering Co and Ni from the leaching solution containing high concentrations of Mn is a challenging problem. In this study, a combination of sulfide precipitation and P507–Cyanex 272 synergistic extraction is proposed for the separation and recovery of Co and Ni from the ARWL solutions of oceanic cobalt‐rich crusts. Under the optimum sulfide precipitation conditions, Co and Ni were precipitated with 99.85% and 99.63% efficiency, respectively, while Mn was coprecipitated with only .79% efficiency. The Co–Ni mixed sulfides were dissolved by dilute sulfuric acid under oxidative conditions to obtain a solution containing 12.584 g/L Co, 11.012 g/L Ni, and a small amount of Mn. Subsequently, Co and Mn were extracted from this solution using P507–Cyanex 272 synergistic extraction, the single‐stage extraction efficiencies of Co and Mn were 95.76% and 99.73%, respectively, and the coextraction efficiency of Ni was 3.02%, under the conditions of a feed solution pH of 3.0, an extractant saponification degree of 70%, a total extractant concentration of 20% (P507 to Cyanex 272 ratio of 3:7), and an O/A ratio of 1.1:1. The results of the thermodynamic study showed that the reaction of Co extraction by this mixed extraction system was exothermic. Ni in the organic phase was washed with an H2SO4 concentration of .12 mol/L, followed by stripping of Co and Mn with an H2SO4 concentration of .6 mol/L. Mn in the stripping solution was removed by oxidative precipitation with (NH4)2S2O8, after which the Co3O4 product was obtained by precipitation with (NH4)2C2O4 and calcination. Similarly, NiC2O4·2H2O can be obtained from the raffinate by (NH4)2C2O4 precipitation. Finally, a flowsheet was developed for the separation and recovery of Co, Ni, Cu, and Mn from the ARWL solutions of oceanic cobalt‐rich crusts. The study provides a promising scheme for the recovery of various valuable metals from deep‐sea cobalt‐rich crusts or manganese nodules.

Microbial-induced MnO2 precipitation in a carbonate coastal aquifer

A study was carried out to identify biogeochemical reactions along a transect of a coastal dolomitic aquifer. In this transect, the physicochemical parameters of the groundwater as well as the microbial composition of samples taken at different depths and salinities were measured. Many of the dissolved ions measured in the groundwater follow a pattern that reflects the distribution of the water masses (fresh, interface and salt) in the aquifer, while others such as Ca and Mg ions deviate from this trend by identifying the zones of maximum dissolution of the carbonate matrix. The concentrations of minor ions, such as Fe and Mn, also follow a singular pattern, with maximum concentrations in the reducing zones of the aquifer and lower values in the oxidizing zones. Precipitates of Mn oxides along with other metals, such as Fe, Ba, Zn and Ni, were observed in the saline zone displaying oxidizing conditions close to the coastline, where a continuous core was recovered. This zone, which is located below the freshwater-seawater mixing zone and features percentages of seawater higher than 80 %, is characterized by the presence of Marinobacter as the predominant genus. These bacteria are also related to the formation of Mn-rich polymetallic oxides in other contexts such as the ocean floor (Wang et al., 2012; Cao et al., 2021). All in all, a biogeochemical reaction model is proposed that describes the formation of these oxides in areas close to the discharge zone of coastal aquifers. To do this, it has been necessary to integrate the results obtained from geochemical, hydrogeological and microbiological information.

Recycling of Valuable Metals from the Priority Lithium Extraction Residue Obtained through Hydrogen Reduction of Spent Lithium Batteries

The selective separation of lithium from spent ternary positive materials is achieved through hydrogen reduction followed by water leaching. Almost 98% of the Li is transformed into soluble LiOH⋅H2O, while the Ni, Co and Mn species are all transformed into insoluble metals or their oxides, so the recovery of Ni, Co and Mn at this stage is challenging. The traditional acid leaching process has drawbacks such as high oxidant consumption, the low recovery of valuable metals and high production costs. Thus, sulfation roasting followed by water leaching was studied in this project. The leaching levels of Ni, Co, Mn and Al reached 87.13%, 99.87%, 96.21% and 94.95%, respectively, with 1.4 times the theoretical amount of sulfuric acid used at 180 °C for 120 min. To avoid the adverse effects of Mn and Al on the quality of the Ni and Co sulfate products, Mn2+ was first separated and precipitated via the KMnO4 oxidation–precipitation method, and >98% of the Mn was removed and precipitated within 30 min with a Kp/Kt (ratio of actual usage to theoretical usage of KMnO4) of 1.0 at pH = 2.0 and 25 °C. After removal of the Mn, the solvent extraction method was adopted by using P204 as an extractant to separate Al. More than 98% of the Al was extracted in 30 min with 20% (v/v) P204 + 10% (v/v) TBP with an A/O ratio of 1:1 at 30 °C. This optimized process for extracting lithium residues improved the hydrogen reduction process of waste lithium batteries and will enable industrialization of the developed processes.

Characteristics of brown zone formed by weathering around fracture in the Hiroshima granite and estimation of iron source for iron oxide precipitation

Characteristics of brown zone formed by weathering around fracture in the Hiroshima granite and estimation of iron source for iron oxide precipitation

Redox control of chromium in the red soils from China evidenced by Cr stable isotopes

With chromium isotopes, we study the intricate dynamics of adsorption and redox processes in soil ecosystems, focusing on chromium's behaviour, in red soil profiles enriched with iron-manganese nodules (FMNs) in South China. Key findings reveal that the primary geological source of chromium in the red soil profiles is the weathering of colluvium parent minerals. FMNs have higher chromium concentrations (325–1451 µg/g) compared to surrounding soils (95–247 µg/g) and display stable δ53Cr values (0.78 ± 0.17‰), indicating their role as stable chromium repositories, reflecting historical processes. Furthermore, by isolating chromium associated with iron oxides (FeO) and silicate minerals (ReS) within FMNs and surrounding soils using CBD extractions, we show that FeO predominantly carry chromium, particularly in FMNs. The δ53Cr values of FeO fractions consistently exhibit heavier signatures than ReS fractions, suggesting the sequestration of isotopically heavy chromium (VI) during Fe oxide precipitation. Fluctuations in soil’s redox, rather than land use, play a pivotal role in controlling the precipitation of Fe oxides in surrounding soils and the formation of FMNs, thus influencing chromium mobility. This highlights the significance of these factors when utilizing chromium isotopic techniques for source tracking in soil systems, contributing to our understanding of chromium's behaviour in soil environments.

Iron oxide fluxing and precipitation in sulphate deposits during heat-resistant alloy corrosion in simulated combustion gas

Two ferritic alloys, Fe-25Cr and Fe-25Cr-2Mn-1Si, and two austenitic alloys, Fe-25Cr-20Ni and 310SS, coated with a thin film of Na2SO4-K2SO4 mixture were exposed to a flowing wet CO2 gas at 650 and 750 °C for up to 300 h. In addition to oxide scaling, a new manifestation of Fe oxide fluxing into the salt layer was observed. The effects of alloy composition and reaction temperature on this phenomenon were determined. The process is attributed to formation of a low melting Na2O-Na2SO4 solution in the early stages of reaction, followed by basic fluxing of FeO and/or Fe3O4.

Synthesis of manganese oxide from manganese ore of bajaur agency khyber Pakhtunkhwa (KPK), Pakistan

In the present work manganese sulphate developed from the Bajaur (KPK, Pakistan) manganese ore was utilized successfully for the synthesized Manganese Oxide chemically by an alkali-oxidation of manganese sulphate using the co-precipitation method. The advantages of this eco-friendly co-precipitation method include quick and easy preparation, simple control of particle size, and cost-effective composition using local ore. Because of the readily available raw materials and the controlled reaction conditions, this method is widely used in industry. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were used to characterize the synthetic manganese oxide. Fourier transforms infrared spectroscopy (FTIR) Infrared reveals that the O-Mn-O vibrational mode occurs in pure manganese oxide at wavelengths between 600 and 500 cm-1. The chemical composition was obtained by EDX analysis and confirmed the presence of Mn and O in the sample. Experimental optimization was done for the manganese oxide precipitation conditions. The findings show that a variety of parameters have an impact on the product yield; the precursor ratio and reaction temperature are the most important variables, and the reaction time and pH value have the greatest impact on the quality of crystallization. Bangladesh J. Sci. Ind. Res. 58(4), 221-230, 2023

Potassium β–alanine – A promising agent for reducing carbon capture cost via electrochemically mediated amine regeneration

Electrochemically mediated amine regeneration (EMAR) for CO2 capture is a promising substitute for traditional organic amine–based CO2 capture by replacing the thermal process with electricity. To avoid problems such as oxidative degradation, toxicity, volatilization, and precipitation of organic amine absorbent, potassium β–alanine was suggested as an absorbent using EMAR process for the first time in this study. The CO2 absorption performance under different copper loading and chemical reactions were studied, and cyclic voltammetry, electrochemical impedance spectroscopy, chronocoulometry and the Taffel extrapolation method were used to study the electrochemical characterization. Compared to the benchmark monoethanolamine (MEA) system, a smaller potential difference between oxidation and reduction peak was acquired in the potassium β–alanine system, of which the energy consumption was only 44.1% of the MEA system at the current of 100 A/m2. The cathode Faraday efficiency in the potassium β–alanine system was 101.9% higher than that in the MEA system at the current density of 25 A/m2. Furthermore, the result of scanning electron microscope of the electrode surface after desorption showed that potassium β–alanine absorbent improved the inhomogeneity of the electrode surface and was in favor of uniform current distribution. Overall, potassium β–alanine can be used as a more environmentally friendly absorbent in the EMAR system and has great potential to further reduce the actual energy consumption and improve the Faraday efficiency and cycling performance.

Ferric Oxyhydroxylsulfate Precipitation Improves Water Quality in an Acid Mining Lake: A Hydrogeochemical Investigation

Hydrogeochemistry of a lignite pit lake in Lusatia, Germany, was investigated. Anoxic groundwater from the dump aquifer rich in FeII (average ~5911 µmol/L) and SO4 (average ~14,479 µmol/L) contents enter the lake as subsurface inflow; oxidation and subsequent precipitation of poorly crystallized Fe-oxyhydroxysulfate (schwertmannite) occurs and causes acidification (pH~2.8). However, the removal of dissolved loads as solid phases significantly improves the groundwater quality of the downgradient as an outflow. The rainwater isotopic values (δD ~−8.88‰ and δ18O ~−65.86‰) closely matched with the groundwater showing very little isotopic modification, which points to a short residence time of groundwater. The displacement of δD and δ18O values (slope = 5.3) from the meteoric water line reflected the evaporative enrichment of the lake water. The isotopic signature also revealed longer residence times of epilimnion than the hypolimnion waters which are dominated by groundwater. The lake is dimictic and showed abrupt changes in physicochemical parameters along the interface (~0.30 m thick) when separating the epilimnion (upper 4 m) from the hypolimnion (bottom 1.5 m). Lake sediments were found to be dominated by clay size fraction occurring as laminations (thickness: 1~0.5 mm) that reflect seasonal sedimentation. Higher schwertmannite formation in the south as compared to the north (recharge side) also serves as a scavenger of potentially toxic elements which is probably a natural solution to man-made problems. Schwertmannite transformation to goethite releases sulfate which is reduced and fixed as secondary sulfide minerals over time. Overall, waters are of a Ca–SO4 to Ca–Mg–SO4 type with distinct inflow (FeII/FeIII > 2.5) and outflow (FeII/FeIII < 0.5) of groundwater.

Co-precipitation of iron and silicon: Reaction kinetics, elemental ratios and the influence of phosphorus

A sufficient supply of dissolved silicon (DSi) relative to dissolved phosphorus (DP) may decrease the likelihood of harmful algal blooms in eutrophic waters. Oxidative precipitation of Fe(II) at oxic-anoxic interfaces may contribute to the immobilization of DSi, thereby exerting control over the DSi availability in the overlying water. Nevertheless, the efficacy of DSi immobilization in this context remains to be precisely determined. To investigate the behavior of DSi during Fe(II) oxidation, anoxic solutions containing mixtures of aqueous Fe(II), DSi, and dissolved phosphorus (DP) were exposed to dissolved oxygen (DO) in the batch system. The experimental data, combined with kinetic reaction modeling, indicate that DSi removal during Fe(II) oxidation occurs via two pathways. At the beginning of the experiments, the oxidation of Fe(II)-DSi complexes induces the fast removal of DSi. Upon complete oxidation of Fe(II), further DSi removal is due to adsorption to surface sites of the Fe(III) oxyhydroxides. The presence of DP effectively competes with DSi via both of these pathways during the initial and later stages of the experiments, with as a result more limited removal of DSi during Fe(II) oxidation. Overall, we conclude that at near neutral pH the oxidation of Fe(II) has considerable capacity to immobilize DSi, where the rapid homogeneous oxidation of Fe(II)-DSi results in greater DSi removal compared to surface adsorption. Elevated DP concentration, however, effectively outcompetes DSi in co-precipitation interactions, potentially contributing to enhanced DSi availability within aquatic systems.

Platinum recycling from fuel cell-spent electrocatalysts using oxidative leaching in HCl solution

The recovery of platinum (Pt) from electrocatalysts in spent proton exchange membrane fuel cells is promising and important for the sustainable development of such a noble metal. Conventional leaching of Pt in the aqueous phase typically requires the use of high concentration of mineral acids and the presence of strong oxidants owing to its thermodynamic stability and non-reactive properties. In the present study, the dissolution of Pt from a Pt/C fuel cell electrocatalyst was investigated using a simple and efficient process under moderate conditions in chloride media. Notably, the leachability of Pt was high ∼76% in a solution of low concentration HCl 2.0 M at 90 °C for 120 min in the absence of an oxidant. The enhancement of Pt leaching efficiency can be obtained using various oxidizing agents HNO3, H2O2, NaClO and NaClO3, and NaClO3 shown the most effective improvement from 76% to 88%. The dissolution of Pt in a solution of 2.0 M HCl and 3.0 wt% NaClO3 improved to 98% by the increase in leaching temperature from 50 to 90 °C. Kinetic studies indicated that Pt leaching in HCl in the presence of NaClO3 followed a chemical-controlled mechanism with an activation energy (Ea) of 40.6 kJ/mol. Based on the findings of this study, an efficient process is proposed to recover and reuse Pt from an electrocatalyst sample of spent fuel cells, including oxidative leaching, chemical precipitation and laser reduction.

Cooperation of ferrous ions and hydrated ferric oxide for advanced phosphate removal over a wide pH range: Mechanism and kinetics

Excessive phosphate loading leads to eutrophication problems in rivers or lakes and causes serious environmental and economic damages, urging new technologies to reduce effluent phosphate at ultra-low levels. As a promising candidate, adsorption over metal oxides is restricted by the released hydroxide anions (OH−) through ligand exchange, which elevates pH and suppresses further adsorption. In this contribution, we found ferrous ions (Fe2+) significantly enhance phosphate removal over hydrated ferric oxide (HFO) in a wide pH range via a cooperation of adsorption and precipitation, and clarified the synergistic mechanism by a series of characterizations and the modified models of adsorption isotherms and pseudo second-order kinetics. The combination of Fe2+and HFO removed up to 51.7 mg/g of phosphate at pH 4.0, with 43.6 and 8.1 mg/g attributing to adsorption and precipitation, respectively. In comparison to HFO alone, HFO/Fe2+ system achieved 2.2-fold increase in phosphate removal, 1.9-fold increase in phosphate adsorption capacity, and 3.4-fold increase in phosphate removal rate. The enhancement is understood by that hydroxide anions released from ligand exchange over HFO are neutralized by protons produced from the oxidative precipitation of ferrous ions. The HFO/Fe2+ combining system is promising to realize advanced removal of low concentration phosphate containing wastewater, and these findings bring new insights for the development of novel phosphate removal technologies through a rational design of a combination process.

Process Development for the Recovery of Manganese Dioxide, Cobalt(II) Sulfate, and Nickel(II) Sulfate Powders from the Reduction Smelted Alloys of Spent Lithium-Ion Batteries

ABSTRACT The smelting reduction of spent lithium-ion batteries at high temperature results in metallic alloys containing cobalt, copper, nickel, and manganese, in addition to aluminum and lithium oxides. A process has been proposed to selectively recover high-purity powders of manganese dioxide, cobalt(II) sulfate, and nickel(II) sulfate from these metallic alloys. Initially, the metallic alloys were completely dissolved using a mixture of 2.0 M sulfuric acid and 15% (v/v) hydrogen peroxide with a pulp density of 25 g/L over a duration of 120 minutes. Subsequently, copper(II) ions were removed through cementation with manganese powder, and aluminum hydroxide was precipitated by adjusting the solution pH to 4.5 at room temperature. Pure manganese dioxide was then obtained from the resulting filtrate through oxidative precipitation, utilizing sodium hypochlorite as an oxidizing agent. The separation of cobalt(II) and nickel(II) was achieved via a two-stage counter-current extraction using a 20% saponified 0.5 M Cyanex 272 solution. The loaded cobalt(II) was stripped using a 0.3 M sulfuric acid solution, leading to the crystallization of cobalt(II) sulfate powders. The pH of the raffinate was adjusted to 9.0, resulting in the precipitation of nickel(II) hydroxide, which was subsequently dissolved to recover nickel(II) sulfate powders from the solution. Most of the experiments were conducted at ambient temperature, except for the evaporation stage of crystallization. Continuous experiments verified that the purity of the recovered cobalt, manganese, and nickel powders was 99.9%.

Strategy for possible separation of light rare earth elements (La, Ce, Pr, Nd) from synthetic chloride solutions by oxidative precipitation, solvent extraction and stripping

Due to their comparable physicochemical characteristics, light rare earth elements (LREEs), such as lanthanum (La), cerium (Ce), praseodymium (Pr), and neodymium (Nd), the separation of these elements is a challenging process. In this study, a strategy involving hydrometallurgical unit operations is presented, including oxidation, precipitation, solvent extraction (SX), and stripping. Separation of Ce(III) can be achieved by selective oxidation with potassium permanganate (KMnO4), which is a strong oxidizing agent and proven to be effective in selectively precipitating Ce(III). By using solvent extraction with 0.5 mol L−1 of Cyanex 572 at an A/O ratio of 1:3 and four stages in a counter-current configuration, La(III) can be separated from Nd(III) and Pr(III) with 100% and 99% extraction, respectively. Cross-current scrubbing with a low concentration of HCl can be used to remove La(III), which becomes the contaminant that is left in the loaded organic. Other mineral acids, including HNO3, H2SO4, and H3PO4 were also investigated as alternative scrubbing/stripping agents.

Revealing the release and migration mechanism of heavy metals in typical carbonate tailings, East China

Refining the occurrence characteristics of tailings hazardous materials at source is of great importance for pollution management and ecological reclamation. However, the release and transport of heavy metals (HMs) from tailings under rainfall drenching in simulated real-world environments is less well portrayed, particularly highlighting the inherent neutralisation in tailings wastes under superimposed dynamic conditions. In this study, dynamic leaching columns simulating actual conditions were used to observe the release and transport of HMs from tailings under acid rainfall infiltration at spatial and temporal scales. The release rate of trace elements (e.g., As, Cr, Ni, Pb, Cd) is high. Neutralisation in the presence of carbonate rocks in the gangue reduces HMs release intensity from tailings with high heavy metal content, along with the precipitation of iron oxides and chromium-bearing minerals, etc. In addition, the vertical differentiation of HMs is more relevant to physical processes. In the absence of carbonate rocks in gangue, the lowest pH value is reached within 1.2 h after acid rain infiltrates the tailings. At the same time, Cu, Zn and Cd are released significantly from the minerals at the superficial level. The release of As(III) is mainly concentrated in the early and late stages of water-rock contact.

Maintaining Excellent Mechanical Properties via Additive Manufacturing of Low-N 25Cr-Type Duplex Stainless Steel.

Duplex stainless steel (DSS) exhibits good mechanical properties and corrosion resistance, and has attracted more and more attention within the fields of both science and technology. However, the increasing levels of N and of Cr, Mo, etc., as alloying elements in DSS increase production difficulty. In particular, the N element increases the risk of Cr2N precipitation, which can seriously deteriorate the thermal plasticity of DSS, while increasing its strength. For this reason, a low-N-content 25Cr-type DSS was designed in order to adapt additive manufacturing processes. With regard to the nano-inclusions of oxide precipitation and effective grain refinement, and considering the benefits of selective laser melting fabrication, a low-N 25Cr-type duplex stainless steel with a 0.09 wt.% N content achieved high mechanical properties, with a yield strength of 712 MPa and an elongation of 27.5%, while the V-notch impact toughness was 160 J/cm2. The microstructure evolution and the reasons behind the improvement in mechanical properties will be discussed in detail.

Digestive fluid components affect speciation and bioaccessibility and the subsequent exposure risk of soil chromium from stomach to intestinal phase in in-vitro gastrointestinal digestion

The simulated in-vitro gastrointestinal method provides a simple way to evaluate the health risk of human body exposed to soil contaminants. Several in-vitro methods have been successfully established for soil As, Pb, and Cd. However, the method development for soil Cr failed up to now, which could be resulted from alteration in the species of Cr (e.g., Cr(VI)/Cr(III)) caused by the gastrointestinal digestion components, ultimately affecting the accessibility of Cr. This study explored the transformation and bioaccessibility of Cr in two Cr-contaminated soils during the physiologically based extraction test. The water-soluble and exchangeable Cr in soil was dissolved in gastrointestinal tract, accompanied with reduction of Cr(VI) into Cr(III), and the reduction occurred after the chemical extraction in two soils rather than during the extraction. Pepsin and organic acids in gastric phase could reduce Cr(VI) into Cr(III) and reduction efficiency were 20.4%− 53.0%, while in intestinal phase, pancreatin and bile salt had little effect on the Cr(VI) reduction, instead, more Cr(VI) was released from soil. In the gastric solution, Cr(VI) was mainly present as HCrO4- and Cr(III) as free Cr3+ ion. In the intestinal phase, Cr(VI) mainly occurred as CrO42- and Cr(III) as Cr(OH)3 (aq). Cr in the soil solid phase was dominated as the precipitates of Cr-Fe oxide, which was hardly extracted. Bioaccessibility of Cr in gastric phase increased as extraction duration increased and decreased in the intestinal phase, the contrary trend was observed for the hazard quotient of Cr in two phases due to Cr(VI)/Cr(III) transformation. This study indicates that the gastrointestinal components could influence the Cr transformation and subsequently affect the Cr bioaccessibility, which would help for a successful establishment of in vitro determination method for soil Cr bioaccessibility.

Determination and prediction of micro scale rare earth element geochemical associations in mine drainage treatment wastes

Acid mine drainage (AMD) has been proposed as a novel source of rare earth elements (REE), a group of elements that includes critical metals for clean energy and modern technologies. REE are sequestered in the Fe–Al–Mn-rich precipitates produced during the treatment of AMD. These AMD solids are typically managed as waste but could be a REE source. Here, results from AMD solids characterization and geochemical modeling are presented to determine the minerals/solid phases that are enriched in REE and identify the mechanism(s) of REE attenuation.AMD solids collected from limestone-based AMD treatment systems were subjected to sequential extraction and synchrotron microprobe analyses to characterize the binding nature of the REE. The results of these analyses indicated REEs were mainly associated with Al or Mn phases. Only selected REE (Gd, Dy) were associated with Fe phases, which were less abundant than Al and Mn phases in analyzed samples. The sequential extractions demonstrated that acidic and/or reducing extractions effectively mobilize REE from the AMD solids evaluated. The observed element associations in solids are consistent with geochemical model results that indicate dissolved REE can be effectively attenuated by adsorption on freshly precipitated Fe, Al, and Mn oxides/hydroxides. The model, which simulates dissolution of CaCO3 and the precipitation of Fe, Al, and Mn oxides with increased pH, accurately predicts the pH dependent accumulation of dissolved REE with Al, Mn, and Fe oxides/hydroxides in the studied AMD treatment systems.The methods and results presented here can be used to identify conditions favorable for accumulation of REE-enriched AMD solids and possible passive or active treatment(s) to extract REE from AMD. This information can be used to design AMD treatment systems for the recovery of REE and is an opportunity to transform the challenges of addressing polluted mine drainage into an environmental and economic asset.

Kinetics of phosphorous sorption to biochar-amended soils

Biochar has been investigated as a potential soil amendment for increasing P sorption to soils. Several studies of shown that coating biochar with Fe oxides can increase the amount of P sorbed to the biochar, yet little is known about the kinetics of P sorption to soils amended with Fe-coated biochar. In this study, the kinetics of P sorption are measured in four soils with contrasting surface properties and textures. In addition, a wood-based biochar, both unmodified (BC) and modified by chemical precipitation of Fe oxides (BCFe), was added to these four soils at a rate of 5% (w/w). P sorption to each soil with and without the unmodified or Fe-coated biochar was measured at incubation times ranging from 1 to 314 h. The data were fit using five different kinetic models to determine if the addition of the BC or BCFe significantly affected the amount of P sorption and the kinetic behavior of P sorption to the biochar-amended soils. Results showed that amending with BC had minimal impact on P sorption to the four soils, whereas the impact of the BCFe on P sorption varied depending on soil. In the low P sorbing soil, the BCFe nearly doubled the amount of P sorbed whereas in the high P sorbing soil, addition of the BCFe resulted in less-than-expected increases in P sorption. For each biochar and soil treatment, the same kinetic model provided the best fit to the observed sorption over time. In two soils, the kinetic model parameters were significantly different following the addition of the BC whereas the model parameters for all four soils were significantly different following addition of BCFe. This study provides new insights into P sorption kinetics to biochar-amended soils.