Iron Precipitation Research Articles

Hydrogen affection on softening and melting behaviours of high alumina sinter in gas-injection blast furnace

As the Al2O3 content increasing in iron ore, some problems presented in blast furnace (BF) processing, such as worsened burden permeability and slag viscosity. Injection of H2 may improve the permeability and reduce the CO2 emission of BF, because of its less density and higher reduction potential when temperature is higher than 820 °C. Therefore, the influence of H2 concentration on the softening and melting behaviour of high alumina sinter is a worth investigate topic. In this article, the high alumina sintering samples with Al2O3 content of 2.11 wt% are investigated in a specially designed experimental apparatus capable of continuously changing pressure on the burden. The results show that the softening temperature range of the samples is expanded and their melting temperature range is reduced with the increasing of H2 concentration from 0 vol% to 20 vol% in reduction gas. But the overall change on softening-melting temperature range is just from 280 °C to 310 °C, which is relatively small comparing with other references reported results. The addition of H2 promotes the reduction of FeO and is conducive to separate between the iron phase and slag phase before the charge droplet formation, which facilitates the aggregation and precipitation of metallic iron in soften state. Simultaneously, higher H2 concentration leads to more pronounced improvements in the permeability of the high alumina burden.

Iron as a precursor of aggregation and vector of organic carbon to sediments in a boreal lake

AbstractWhile organic matter (OM) interactions in the water column prevent iron (Fe) precipitation and sedimentation, Fe also acts as a precursor of aggregation and a vector of OM to sediments. This study aims to characterize Fe–OM interactions to understand the role of Fe in promoting aggregation and transport of OM. Samples of Fe and OM were collected from water, settling material, and sediment along a gradient starting from the inlet and continuing offshore within a boreal lake. Fe speciation was determined using X-ray absorption spectroscopy (XAS), and the chemical composition of OM was assessed using Diffuse reflectance infrared Fourier transform spectroscopy (DRIFT IR) and Nuclear magnetic resonance spectroscopy (NMR). The results show a decrease in Fe and OM concentrations in the water column with increasing distance from the inlet. Winter sampling revealed a shift in Fe speciation from dominance of organically complexed Fe to an increase in Fe(oxy)hydroxide, accompanied by a loss of aromatic and carboxylate function of OM. Summer sampling revealed no significant changes along the gradient, with Fe(oxy)hydroxide and carbohydrates dominating the water phase. Interestingly, settling particles and surface sediments were dominated by Fe(oxy)hydroxides and aliphatic OM. We propose that phototransformation may be an important process that influences the interaction between Fe and OM and, as a consequence, their fate along the spatial gradient. Our study suggests a photochemically induced loss of carboxylate groups, reflected by an increased carbohydrate-to-carboxylate ratio along the gradient, particularly in winter, and generally lower levels during summer. Loss of carboxylate function promotes the formation of Fe(oxy)hydroxides, which in turn, facilitates the aggregation and sinking of OM, particularly aliphatic components. These insights contribute to a broader understanding of carbon cycling and storage in lakes. Future studies should assess the significance of photochemical processes to OM burial and it how may change given trends in Fe and OM in northern regions.

Sustainable ferritin from bovine by-product liver as a potential resource: Ultrasound assisted extraction and physicochemical, structural, functional, and stable analysis

Ferritin is an iron-containing protein that is widely present in all organisms and has the function of regulating the metabolic balance of iron in organisms. It can be separated from animal by-product tissues and converted into value-added components to promote the development of a circular economy. This study established a method for extracting bovine liver ferritin (BLFer) using ultrasound-assisted buffer system. The optimal extraction conditions were determined through single factor and response surface optimization experiments as follows: ultrasound temperature of 70 °C, extraction time of 25 min, ultrasonic power of 400 W and solvent-to-solid ratio of 2 mL/g, the experimental value of the ferritin yield was 32.18 ± 0.12 g/kg. Compared with traditional methods, Ultrasound-assisted extraction improved the ferritin yield and enhanced its structural stability. Bioinformatics analysis revealed that BLFer is a hydrophilic protein with strong thermal stability. The BLFer has a ferrous oxidase active center, which plays an important role in the oxidative precipitation and reductive release of iron. It can dissociate under strong acids or bases but maintains good stability after heat treatment. These findings will help improve the comprehensive utilization of animal by-products, and promote the potential application of animal by-product ferritin in food and other industries.

Removal of iron and aluminum from hydrometallurgical NMC-LFP recycling process through precipitation

There is a need to develop removal strategies for typical battery impurities–iron and aluminum–from actual hydrometallurgical recycling solutions. In this work, the investigated solution originated from lithium nickel manganese cobalt oxide (NMC) rich black mass, while iron phosphate (LFP) was used as an in situ reductant. It was found that the presence of phosphate ions supported selective iron precipitation already at pH = 2.0 (T = 60 °C, t = 3 h, NaOH), with nearly complete iron removal (97.8 %). The precipitate was rich in iron (21.5 wt%) and phosphorus (13.4 wt%); it also contained 0.7 wt% Ni and 0.3–0.4 wt% Mn, Co, Al, and Li. It is suggested that the presence of phosphate in minor amounts may cause this co-precipitation of battery metals. With the aim of combined precipitation of iron (100 %) and aluminum (91.0 %), the pH was increased up to 4.5. Although 90.8 % of fluoride precipitated, the remaining fluorides may have kept the aluminum partially in soluble form as Al-F complexes. The formed precipitate had lower iron (18.4 wt%) and phosphorus (11.4 wt%) content, whereas the impurity contents and thus the battery metals losses were slightly higher: Ni, Mn, Co, Al, and Cu were each between 1.1–1.9 wt% and Li and F < 1 wt%. In the precipitates investigated, iron was found predominantly as iron phosphate (FePO4), whereas a minor fraction also precipitated as iron fluoride (FeF3). The precipitated aluminum existed mainly as AlOOH. The results presented here will help to build iron and aluminum removal strategies for industrial battery recycling solutions, and also provide insights into the dominant iron and aluminum phases forming the precipitates.

Effect of manganese(II) and magnesiumg(II) in zinc acid leaching solution on iron precipitation via the hematite process

Abstract Iron (Fe) removal is a critical step in the hydrometallurgical zinc (Zn) extraction process. Hematite, a stable Fe precipitate, offers an environmentally friendly option that complies with environmental protection standards. While existing research primarily focuses on hematite process technology, there is a lack of studies on how ions in ZnSO4 leaching solutions affect Fe removal efficiency and hematite particle size distribution. This study investigated the influence of manganese II (Mn(II)) and magnesium II (Mg(II)) concentrations and temperature on both Fe removal efficiency and hematite particle size distribution in ZnSO4 leaching solution. The results indicated that at various temperatures, the highest Fe removal efficiency occurred with an initial Mn(II) concentration of 10 g/L and an Mg(II) concentration of 15 g/L. As the concentrations of Mn(II) and Mg(II) as well as temperature increased, FeSO₄ crystallization also increased, which adversely affected hematite precipitation. The average particle size of hematite decreases from 300 to 100 nm, resulting in a more uniform particle size distribution, which correlated with the homogeneous solution saturation precipitation mechanism. However, the number of rod-shaped, regular small particles decreases, while the number of irregular, blocky particles increased.

Characterisation of growth parameters for the extremely acidophilic archaeon Ferroplasma acidiphilum DSM 12658 using a two-step turbidimetric growth measurement method

The acidophilic archaeon Ferroplasma acidiphilum exhibits remarkable adaptations to life in highly acidic environments. Nevertheless, the investigation of its molecular biology is challenging because of the slow growth of the organism, low biomass yield, and limitations of standard growth measurement techniques caused by iron oxidation.•A novel two-step turbidimetric growth measurement (2TGM) method was developed to address the shortcomings associated with iron precipitation in culture media. The method comprises two distinct preparation steps.•The initial 2TGM step involves centrifuging culture samples at high speed to remove F. acidiphilum cells and iron precipitates, thus preparing a blank.•The second 2TGM step involves centrifuging the culture at a lower speed with the objective of selectively removing iron precipitates, thus allowing F. acidiphilum cells to remain suspended in the supernatant. This preparation enables subsequent measurement of cell density.A study on the growth of F. acidiphilum showed a standard logistic pattern with a 35-h lag phase, approximately 9-h doubling time, and 0.042 OD carrying capacity. A new two-step turbidimetric growth measurement (2TGM) method overcomes limitations of existing approaches, enabling further investigation of F. acidiphilum.

Assessment of water supply to the east European arctic agglomeration from groundwater, taking into account their quality and health risks

The purpose of the study is to assess the possibilities of using groundwater for water supply in the East European Arctic agglomeration based on an assessment of their quality and health risks. For this purpose, high-precision determinations of the complete macro- and microcomponent composition were carried out in sixty-six water samples taken from wells up to 180 m deep. It was found that in some samples the concentrations of Na+, Fe, B, Ba, Mn and U exceeded WHO standards. The least mineralized young waters are characterized by the processes of dissolution of carbonates with the transition of Ca, Mg, Ba, Sr into water, and the processes of leaching of Fe and Mn by acidic swamp waters from near-surface sediments. Waters of high mineralization, enriched in Na+, Cl-, B, Mo, Cd, Pb, were formed as a result of the dissolution of aluminosilicate rocks over thousands of years and mixing with relics of ancient and modern marine transgressions. An assessment of the average Water Quality Index value of the studied aquifer showed that, in general, the water is of excellent quality. Non-carcinogenic risks were determined primarily by uranium concentrations. The average danger index values for this element for children were 1.22. In adults it was slightly lower and amounted to 0.83. Carcinogenic risks are associated primarily with arsenic concentrations. The average total carcinogenic risk associated with this element was 3.8.10−5, which is acceptable, but samples from two wells showed total carcinogenic risk values above 10−4, which is in the high-risk area. For drinking purposes, it is preferable to use low-mineralized water with a minimum content of toxic elements. If necessary, preliminary aeration of the water is possible, during which precipitation of iron, arsenic and uranium occurs. Due to the typical nature of the problem under consideration for the Arctic regions, the results obtained can be used at other sites in the Subpolar zone.

Enhanced degradation of 2,4-DCP in a bicarbonate-modified Fenton with EDTA under near-neutral conditions

To address the issues of low pH requirements and low active iron content in the traditional Fenton system, bicarbonate in this study was presented in Fenton system to form HCO4− through reaction with hydrogen peroxide (HCO3––H2O2, BAP) and activated by FeⅡ-EDTA to enhance the degradation of 2,4-DCP under near-neutral conditions. 2,4-DCP can be totally degraded after 60 min of reaction at pH of approximately 6.4 under the optimal concentrations of Fe2+, NaHCO3 and EDTA-2Na of 4 mmol·L−1, 10 mmol·L−1 and 2 mmol·L−1, respectively. In addition to serving as a reactant in the reaction between bicarbonate and hydrogen peroxide to form the intermediate HCO4−, bicarbonate also functions as a pH buffer to bring the solution’s pH closer to neutral. The introduction of EDTA-2Na can effectively inhibit iron precipitation to promote maintaining the existence of Fe in dissolved form, improving the catalytic capacity of the system and reduce the dosage of Fe2+. The primary involvement of ·OH in the reaction process was validated by free radical quenching studies and EPR testing; the contributions of 1O2 and O2·− were very small.

Studies of the Morphology of Hematite Synthesized from Waste Iron Sulfate.

Microwave-based reactions have gained traction in recent years due to their ability to enhance reaction rates and yield while reducing energy consumption. Also, according to the conception of 'waste to materials', various waste feeds are intensively sought to be tested. The experimental setup of this study involved varying pH levels, oxidation agents, and precipitation agents to optimize the synthesis process of iron red based on waste iron sulfate. The selection of oxidation and precipitation agents was found to significantly influence the pigment synthesis process. Various oxidizing agents, including hydrogen peroxide and atmospheric air, were evaluated for their effectiveness in promoting the oxidation of ferrous ions to ferric ions, essential for pigment formation. Additionally, different precipitation agents such as sodium hydroxide and ammonia solution were assessed for their ability to precipitate iron hydroxides and facilitate pigment particle formation. The characterization of synthesized pigments revealed promising results in terms of quality and color properties. Helium Ion Microscopy (HIM) analysis confirmed the formation of well-defined pigment particles with controlled morphology. X-ray diffraction (XRD) studies provided insights into the crystalline structure of the pigments, indicating the presence of characteristic iron oxide phases. By improving this technology, waste iron sulfate can be efficiently transformed into valuable iron pigments, offering a sustainable solution for waste management while meeting the growing demand for high-quality pigments.

Enhanced nitrogen and phosphorus removal by iron-manganese mediated autotrophic denitrification in electrochemical system and the underlying mechanisms

At present, the research on Fe/Mn autotrophic denitrification is very limited, and the underlying mechanism in electrochemical system is not clear. In this study, an electrochemical system based on Fe-Mn autotrophic denitrification was constructed for the treatment of low C/N wastewater. The underlying mechanism and electrochemical process of Fe/Mn-mediated autotrophic denitrification were elucidated. The results showed that pyrite and manganese mineral matrix had no significant effect on COD removal, but had significant effect on nitrogen removal. R1 (activated carbon matrix) had the lowest nitrogen removal rate, with an average of 66.06 %. The mean removal rate of R2 (iron matrix) and R3 (manganese matrix) were 93.94 % and 95.89 %, respectively. The coupling of iron/manganese ammoxidation and autotrophic denitrification was the main mechanism to achieve efficient nitrogen removal. ICP and FIRT results showed that strong REDOX reactions of Fe, Mn and sulfur occurred at the anode of MFC. Direct precipitation of iron and manganese and electrochemical flocculation (FeOOH) effectively improved phosphorus removal. The phosphorus removal rates of R2 and R3 reached 93.89 % and 95.85 %, respectively. R3 has high electron transfer efficiency with a maximum voltage of 680 mV. Metagenomic analysis showed that 19 important transcripts associated with nitrogen metabolism pathways and 4 nitrogen metabolism pathways were detected. Enzymes encoded by nap A and nar G genes were abundant in R3 system. Reductase encoded by nrfA and nrfH genes was abundant in R2 system. Iron REDOX genes iroE, iroN, oorA, and manganese REDOX genes moxR, moxA were detected. The results of metabolic pathways and related enzymes further revealed the coupling cycle relationship between metal elements and nitrogen, phosphorus and sulfur in electrochemical systems. This study can not only provide a new method for efficient nitrogen and phosphorus removal of sewage, but also provide scientific basis for improving the geochemical cycle of metal elements and nitrogen elements.

Unveiling the Mechanism in Nickel Loss During the Neutralization of Pregnant Acid Leach Solution by Various Alkaline Chemicals Using Electron Imaging, X-Ray Diffraction, and Electron Energy Loss Spectroscopy Analyses

ABSTRACT Removal of iron and aluminum from nickel-bearing pregnant leach solution is imperative prior to recovering nickel. However, the mechanisms into the loss of both nickel and cobalt in precipitate products during the neutralization process remained unclear and debatable. In this study, the precipitation ratios of nickel, as well as other valuable metals in iron precipitate products, were investigated by examining bulk and surface properties of iron precipitates using X-ray diffraction, infrared spectroscopy, scanning electron microscopy, and electron energy loss spectroscopy. Amorphous ferrihydrite was identified as the major phase for iron precipitates. Over 99% precipitation ratio for iron and aluminum was achieved at pH 3. The loss of nickel in iron precipitates was strongly dependent on solution pHs, and the losses of nickel were found to be 3%, 8%, and 28% at pHs of 3, 4, and 5, respectively. The type of alkaline chemicals impacted the mineralogical composition of iron precipitate products and loss of valuable metals but had a minor impact on iron precipitation ratio. This work revealed three major mechanisms for the loss of nickel and cobalt during iron precipitation process: (1) entrainment of nickel-bearing PLS in filtered products, (2) surface adsorption on iron precipitates, and (3) lattice incorporation of nickel in iron precipitates. Additionally, the result of desorption experiments by H+ and Na+ ions showed that approximately 55–85% of lost nickel was incorporated within the lattice structure of iron precipitates, while the degree of nickel incorporation depends on the type of neutralizing reagents, precipitation conditions, and washing media.

Groundwater well rehabilitation using hydropuls method: a case study in wonosobo groundwater well

Abstract Hydropuls is one of the groundwater well rehabilitation methods that involves pulsing highly compressed nitrogen gas through screen pipes at an adjustable interval. Nitrogen gas was chosen because of its colorless, odorless, and inert properties. The aquifer lithology of this groundwater well is sand, gravel and breccias (member of Sundoro Volcanics; Qsu) with silty clay as the impermeable layer that makes the aquifer type is confined aquifer. The following methods were used in this well rehabilitation: step tests before, borehole camera before, hydropuls, airlifting, borehole camera after and step test after well rehabilitation. Thin section analysis shows that sediment mostly consists of lithic fragments and plagioclase. The results of the polished section analysis reveal that most of the metallic minerals are magnetite and hematite. The XRF results show that the sediment mostly consists of SiO2, Al2O3 and Fe2O3. According to the XRD results, the sediment is mostly albite. The interpretation of sediment analysis shows that the clogging is caused by iron precipitation. The result is an average increase in specific capacity of 1.43 l/s/m (a 168% increase over the initial conditions) and an average drawdown improvement of 2.56 m (a 114% improvement compared to pre-hydropuls conditions). Borehole camera imaging confirmed that the precipitation on the screen was removed and the screen is in good condition.

Alternatywne podejście do usuwania/odzyskiwania wybranych metali z wody kopalnianej wypływającej z zalanej kopalni syderytu Nižná Slaná

The objective of this work was the application of innovative method for metals recovery from metalliferous mine water released from the flooded siderite ore deposit Nižná Slaná. Although the metals contained in mine drainage are considered environmental pollutants, they may also be recognised as valuable resources. Several techniques can be used to obtain them by precipitation. Conventional processes using alkaline reagents produce huge amounts of mixed sludge with appropriate storage and management requirement, void of possibility of individual metals subsequent processing. This study examined the feasibility of Fe and Mn selective retrieval from real mine water. After oxidation and partial precipitation of iron using hydrogen peroxide, precipitation by sodium hydroxide was applied to the residue iron removal from mine water. In the next step potassium permanganate was used to eliminate manganese by oxidative precipitation. ORP and pH values of processed mine water was recorded in the course of oxidation/precipitation processes. The morphology and elemental composition of obtained products were studied by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). The recovery efficiencies of Fe and Mn from mine water reached 99.87 % and 99.25%, respectively. Target metals were removed with high selectivity to levels that comply with environmental requirements.

Efficient Recycling and Utilization Strategy for Steel Spent Pickling Solution

Before steel can be utilized, pickling is necessary to remove surface oxidation products. However, as the ferrous ion concentration in the pickling solution increases, the pickling rate significantly diminishes, necessitating the treatment of spent pickling solution (SPS) to mitigate its hazardous effects prior to disposal. Current industrial methods predominantly rely on neutralization and precipitation techniques, which are cost-prohibitive and generate substantial by-products, thus failing to meet environmental protection standards. In this study, a new method, which is based on the formation of FeC2O4·2H2O precipitate in a strong acid solution, is proposed to treat the SPS. Initially, the SPS undergoes a two-step impurity removal process, followed by the controlled addition of oxalic acid dihydrate (H2C2O4·2H2O) to precipitate iron. The resulting precipitate is filtered, washed, and vacuum-dried, and the regenerated acid is recycled back into the pickling tank. When 1 g/10 mL of H2C2O4·2H2O is used, the iron removal rate achieves 60%, and the acidity of the regenerated acid increases by 11.3%. X-ray diffraction pattern (XRD) and thermogravimetric–differential scanning calorimetry (TG-DSC) characterization showed that the precipitate was α-FeC2O4·2H2O, with an average particle size of about 3.19 μm and a purity of 95.24%. This process innovatively achieves efficient recycling of acid and iron resources, offering a potential solution to the industrial challenge of difficult SPS treatment in the steel industry and meeting the urgent need for sustainable development.

Process Design for Direct Production of Battery Grade Nickel Sulfate

The clean energy transition has increased the global demand of nickel sulfate used in the Li-ion batteries. A short-term solution is to refine the nickel sulfate product from nickel intermediates. In the long-term, new direct nickel sulfate production technologies are needed. This research focused on the modeling-based concept development of a novel direct hydrometallurgical nickel sulfate process consisting of chemical leaching, impurity removal by precipitation, solvent extraction, and crystallization as an alternative to the conventional nickel sulfate production route via a nickel matte intermediate. The conventional process route with the studied nickel concentrate had lower chemical consumption and waste production compared to direct hydrometallurgical process where approximately 60% of iron was leached consuming oxygen, and the following iron precipitation step consuming calcium carbonate resulted in a high amount of iron precipitate together with gypsum. However, hydrometallurgical alternatives are often suitable for lower ore grades or volumes and can recover copper as by-product metal. The biggest impacts on carbon footprint from chemical consumption in the direct hydrometallurgical process were generated in iron precipitation and oxygen use in leaching. With the studied nickel concentrate, pyrrhotite played a key role in both oxygen use and iron precipitation. In the leaching step, 68% of total oxygen consumption was related to pyrrhotite leaching, while in iron removal 73% of total iron originated from pyrrhotite. Thus, especially pyrrhotite removal prior to leaching needs to be developed to reduce the carbon dioxide footprint, when the pyrrhotite content in the material is high.Graphical

Chronoamperometric investigations on electrochemical synthesis of iron nitrides in molten salt system

A systematic investigation of the electrochemical iron nitride synthesis in a LiCl/KCl salt melt at 723 K shows an optimum of ϵ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\epsilon$$\\end{document}-Fe3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_3$$\\end{document}N1+x\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{1+x}$$\\end{document} formation in the range of 2.2 to 2.3 V and for γ′\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\gamma '$$\\end{document}-Fe4\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_4$$\\end{document}N between 2.4 and 2.5 V enabling the control of the desired iron nitride phase by setting the supplied terminal voltage. The product formation of iron nitrides starts when the electrochemical window is reached, which could be verified by linear sweep voltammetry. Hence, a maximum of nitrogen content in the formed iron nitride phases is observed for 2.27 V. During elongated synthesis periods, convection emerges as the predominant transport mechanism hindering an accelerated reaction rate with higher overpotential applied. Real-time analysis of the background current allows conclusions about the remaining nitride concentration. Additionally, there is concurrent iron nitride formation at the electrode surface through nitride adsorption and autonucleation-induced precipitation of iron and nitride ions. The analysis of the amount of sediment in comparison to the layer thickness of the nitrided working electrode suggests that the autonucleation mechanism dominates over the adsorption mechanism with increasing overpotential and can be further enhanced by this feature.Graphical abstract

New methodological approach for deep penetrating geochemistry and environmental studies, Part 2: field determination of Co(II)/Ni(II) and Pb(II)/Zn(II) of on-site soil extractions by electrochemical stripping techniques

In the framework of deep penetrating geochemistry for mineral exploration, we report a field electroanalytical method using disposable screen-printed working electrodes able to quantify metal pathfinders in partial extracts of soil samples at the nanomolar level on-site. Four metal pathfinders (Co, Ni, Pb and Zn) were chosen due to their geological interest and suitability of electrochemical detection. Square-wave anodic stripping voltammetry (SW-ASV) was developed for the simultaneous detection of Pb(II) and Zn(II) providing limits of detection (LOD) of 1.2 and 5.3 nM, respectively. A linear-scan cathodic stripping voltammetry (LS-CSV) methodology was developed for the joint detection of Co(II) and Ni(II) yielding LOD of 1.8 and 3.5 nM, respectively. Method validation was carried out on 14 upper B-horizon soil samples during a field survey. Two wet extraction procedures were applied for soil samples – a strong extraction using nitric acid (HNO 3 ) and a weak extraction using calcium chloride (CaCl 2 ). Excellent agreement between electroanalytical methods and inductively coupled plasma mass spectrometry (ICP-MS) was found for Pb(II), while a small underestimation was observed for Zn(II). For Co(II) and Ni(II) the LS-CSV measurements in the HNO 3 extractions were impossible due to the change from low pH to pH to 7.15 which induces precipitation of iron and aluminium. For the CaCl 2 extractions, the Co(II)/Ni(II) results obtained by LS-CSV were in excellent agreement with ICP-MS measurements.

Organic-inorganic hybrid interfaces with π-d electron coupling for preventing metal and sulfur leaching toward enhanced oxygen evolution reaction

Transition metal sulfides (TMSs) catalysts with high catalytic oxygen evolution reaction (OER) activity have been extensively studied, especially Fe and Co-based sulfides. Fe and Co active sites with a strong synergistic effect, which can adjust the electron density distribution and effectively improve the electrocatalytic OER activity. However, TMSs have poor stability in alkaline environment caused by metal ions and sulfur elements are facilitated to dissolve. In this work, TMSs was modified by polyaniline (PANI) to inhibit the precipitation of iron, cobalt, and sulfur elements and enhance its stability under alkaline conditions. Moreover, π-d structure can also be formed by the coating of PANI, which can further adjust its own electronic structure on the basis of stabilizing the TMSs structure, so as to improve the electrochemical performance, rendering them to stably operate at harsh environment for more than 90 h. These findings offer new guidance for improving the electrocatalytic stability of TMSs.

Permeability–porosity model considering oxidative precipitation of Fe(II) in granular porous media

Despite decades of research into the interactions between groundwater and seawater, the evolution of permeability produced by iron precipitation has received little attention, resulting in uncertain predictions of permeability in porous media. This study establishes a novel permeability–porosity model for estimating permeability considering the oxidative precipitation of Fe(II) in granular porous media. The accuracy of this model is validated by a series of sand column tests investigating iron precipitation driven by subsurface freshwater–saltwater mixing. The experiments showed a localized pattern of iron precipitation concentrated near the freshwater–saltwater interface in those columns, where a low-permeability zone with intensive precipitation was generated, subsequently leading to a decrease in sand permeability of 45%. Extracted samples analyzed by scanning electron microscopy showed quartz sand particles coated by iron precipitates. With those successful experiments, the newly developed model is validated and fully capable of estimating the sand permeability underlying this geochemical process, providing predictions to within an order of magnitude. The present experimental results and model predictions bring valuable insights into how the pore matrix of a granular porous media evolves during iron precipitation in the subsurface groundwater–seawater mixing zone.

Selective Gold Precipitation by a Tertiary Diamide Driven by Thermodynamic Control.

The simple diamide ligand L was previously shown to selectively precipitate gold from acidic solutions typical of e-waste leach streams, with precipitation of gallium, iron, tin, and platinum possible under more forcing conditions. Herein, we report direct competition experiments to afford the order of selectivity. Thermal analysis indicates that the gold-, gallium-, and iron-containing precipitates present as the most thermodynamically stable structures at room temperature, while the tin-containing structure does not. Computational modeling established that the precipitation process is thermodynamically driven, with ion exchange calculations matching the observed experimental selectivity ordering. Calculations also show that the stretched ligand conformation seen in the X-ray crystal structure of the gold-containing precipitate is more strained than in the structures of the other metal precipitates, indicating that intermolecular interactions likely dictate the selectivity ordering. This was confirmed through a combination of Hirshfeld, noncovalent interaction (NCI), and quantum theory of atoms in molecules (QTAIM) analyses, which highlight favorable halogen···halogen contacts between metalates and pseudo-anagostic C-H···metal interactions in the crystal structure of the gold-containing precipitate.