Rapid Oxidative Dissolution of Zerovalent Iron Induced by Sulfite for Efficient Removal of Arsenate and Arsenite: Selective Formation of Scorodite.

In this study, we proposed a moderate oxidation strategy for accelerating the oxidative dissolution of zerovalent iron (ZVI) using sulfite (S(IV)), thereby improving the removal of As(V) and As(III). Results revealed that, in the presence of 2.0 mM S(IV), both As(V) and As(III) were selectively converted into scorodite at pH0 3.0-7.0, while As(III) oxidation and As(V) immobilization were impressed over pH0 8.0-10.0. Batch experiments, radical quenching experiments, and electron spin resonance (ESR) measurements demonstrated that ZVI initially boosted S(IV) activation to generate SO4•-, •OH, and protons, and in turn, ZVI was further oxidized more intensely by these radicals than by oxygen. Concurrently, substantial protons derived from S(IV) oxidation neutralized hydroxyls produced by ZVI oxidation, maintaining an acidic environment conducive to the generation of scorodite rather than iron (hydr)oxides. Characterizations of X-ray diffraction (XRD), Raman, attenuated total reflectance-Fourier transform infrared (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS), field emission scanning electron microscopy (FESEM), and high-resolution transmission electron microscopy (HRTEM) confirmed that scorodite was formed in situ and then exfoliated from the surface of ZVI, and approximately 75% of ZVI could still be recovered, which contributed to efficient As removal in successive runs and real As-polluted wastewater. The application of S(IV) achieved a balance among ZVI reactivity improvement, As(V)/As(III) removal, and raw material consumption, making it a promising approach for addressing arsenic contamination in wastewater treatment.

Local Structure and Crystallization Transformation of Hydrous Ferric Arsenate in Acidic H2O-Fe(III)-As(V)-SO42- Systems: Implications for Acid Mine Drainage and Arsenic Geochemical Cycling.

Hydrous ferric arsenate (HFA) is a common thermodynamically metastable phase in acid mine drainage (AMD). However, little is known regarding the structural forms and transformation mechanism of HFA. We investigated the local atomic structures and the crystallization transformation of HFA at various Fe(III)/As(V) ratios (2, 1, 0.5, 0.33, and 0.25) in acidic solutions (pH 1.2 and 1.8). The results show that the Fe(III)/As(V) in HFA decreases with decreasing initial Fe(III)/As(V) at acidic pHs. The degree of protonation of As(V) in HFA increases with increasing As(V) concentrations. The Fe K-edge extended X-ray absorption fine structure and X-ray absorption near-edge structure results reveal that each FeO6 is linked to more than two AsO4 in HFA precipitated at Fe(III)/As(V) < 1. Furthermore, the formation of scorodite (FeAsO4·2H2O) is greatly accelerated by decreasing the initial Fe(III)/As(V). The release of As(V) from HFA is observed during its crystallization transformation process to scorodite at Fe(III)/As(V) < 1, which is different from that at Fe(III)/As(V) ≥ 1. Scanning electron microscopy results show that Oswald ripening is responsible for the coarsening of scorodite regardless of the initial Fe(III)/As(V) or pH. Moreover, the formation of crystalline ferric dihydrogen arsenate as an intermediate phase at Fe(III)/As(V) < 1 is responsible for the enhanced transformation rate from HFA to scorodite. This work provides new insights into the local atomic structure of HFA and its crystallization transformation that may occur in AMD and has important implications for arsenic geochemical cycling.

Mechanism and thermodynamics of scorodite formation by oxidative precipitation from arsenic-bearing solution.

Arsenic pollution is a challenging environmental issue caused by arsenic-bearing wastes from nonferrous metallurgy. Oxidative precipitation via introducing O2 into an ionic Fe(II)-As(V) solution is an advanced method for arsenic immobilization. However, the underlying mechanism is still not well understood. This study proposed a mechanism for scorodite formation by oxidative precipitation, and its thermodynamics were calculated using Gaussian software. Scorodite formation was divided into three stages: precursor formation (3-90 min), oxidative conversion (90-270 min) and crystallization (270-720 min) from the variation in precipitates and solution characterization and parameters such as initial pH, arsenic concentration, and ferrous dosage. In the scorodite formation mechanism, the precursors originate from the coordination polymerization of aqueous Fe(H2O)62+ and H2AsO4-, which contributes to the oxidative conversion of coordinated polymers ([Fe(H2O)4(H2O)]nn+) to basic Fe(H2O)2AsO4 until regular octahedral crystals are formed via nucleation and growth during crystallization. The ΔrGmθ for polymerization varied from -491.96 kJ mol-1 to -33.30 kJ mol-1, and the ΔrGmθ of oxidative conversion changed from -982.16 kJ mol-1 to -224.82 kJ mol-1, demonstrating the feasibility in scorodite formation. This research is significant for understanding scorodite formation in As(V) solutions. It can provide schemes for controlling and modifying the conditions of arsenic-bearing waste immobilization in the laboratories and industries.

Application of dirty-acid wastewater treatment technology in non-ferrous metal smelting industry: Retrospect and prospect.

Dirty-acid wastewater (DW) originating from the non-ferrous metal smelting industry is characterized by a high concentration of H2SO4 and As. During the chemical precipitation treatment, a significant volume of arsenic-containing slag is generated, leading to elevated treatment expenses. The imperative to address DW with methods that are cost-effective, highly efficient, and safe is underscored. This paper conducts a comprehensive analysis of three typical methods to DW treatment, encompassing technical principles, industrial application flow charts, research advancements, arsenic residual treatment, and economic considerations. Notably, the sulfide method emerges as a focal point due to its minimal production of arsenic residue and the associated lowest overall treatment costs. Moreover, in response to increasingly stringent environmental protection policies targeting new pollutants and carbon emissions reduction, the paper explores the evolving trends in DW treatment. These trends encompass rare metal and sulfuric acid recycling, cost-effective H2S production methods, and strategies for reducing, safely disposing of, and harnessing resources from arsenic residue.

Immobilizing arsenic-enriched wastewater from utilization of crude antimony oxides as scorodite using a novel multivalent iron source.

Arsenic-enriched wastewater (A-EW) is a hypertoxic sewage from the utilization of crude antimony oxides in lead anode slime metallurgy. In traditional methods, the H+ accumulation inhibits the arsenic immobilization during scorodite synthesis. In this study, a novel multivalent iron source comprised of Fe(OH)3 and FeSO4·7H2O was proposed to resolve the adverse effects of pH fluctuation during immobilizing A-EW as scorodite. Various approaches, such as scanning electron microscopy and X-ray photoelectron spectroscopy, were applied to characterize the synthesized scorodite. This work was divided into two parts. In thermodynamics, HnAsO4(3-n)- (n = 1, 2, 3) and Fe(OH)n(3-n)+ (n = 0, 1, 2, 3) can feasibly coprecipitate as scorodite according to their △rGm,Tθ ranged from -111.10 kJ mol-1 to -33.53 kJ mol-1. In experimental research, A-EW was immobilized as scorodite by optimizing conditions as initial pH = 2.0, molar ratio of Fe to As = 1.2, molar ratio of Fe(II) to Fe(III) = 4:6, arsenic concentration = 40 g/L, and temperature = 95 °C. The arsenic precipitation ratio is 99.60%, and the micromorphology of synthesized scorodite presents a regular octahedron having size of 5-10 µm. The low leachability of As (0.41 mg/L) in toxicity characteristic leaching procedure (TCLP) confirmed that the prepared scorodite is nonhazardous. The solution pH is stable at 2.0 as the H+ depletion (0.5660 mol) by Fe(OH)3 dissolution and Fe2+ oxidization balanced with that (0.5657 mol) generated from As(V)-Fe(III) coprecipitation. In general, the A-EW was effectively immobilized by proposed multivalent iron source, and can be potentially applied to safely dispose other industrial effluents, such as high arsenic leachates and arsenic-bearing waste acid from nonferrous metallurgy.

Arsenic release from microbial reduction of scorodite in the presence of electron shuttle in flooded soil.

Scorodite (FeAsO4·H2O) is a common arsenic-bearing (As-bearing) iron mineral in near-surface environments that could immobilize or store As in a bound state. In flooded soils, microbe induced Fe(III) or As(V) reduction can increase the mobility and bioavailability of As. Additionally, humic substances can act as electron shuttles to promote this process. The dynamics of As release and diversity of putative As(V)-reducing bacteria during scorodite reduction have yet to be investigated in detail in flooded soils. Here, the microbial reductive dissolution of scorodite was conducted in an flooded soil in the presence of anthraquinone-2,6-disulfonate (AQDS). Anaeromyxobacter, Dechloromonas, Geothrix, Geobacter, Ideonella, and Zoogloea were found to be the dominant indigenous bacteria during Fe(III) and As(V) reduction. AQDS increased the relative abundance of dominant species, but did not change the diversity and microbial community of the systems with scorodite. Among these bacteria, Geobacter exhibited the greatest increase and was the dominant Fe(III)- and As(V)-reducing bacteria during the incubation with AQDS and scorodite. AQDS promoted both Fe(III) and As(V) reduction, and over 80% of released As(V) was microbially transformed to As(III). The increases in the abundance of arrA gene and putative arrA sequences of Geobacter were higher with AQDS than without AQDS. As a result, the addition of AQDS promoted microbial Fe(III) and As(V) release and reduction from As-bearing iron minerals into the environment. These results contribute to exploration of the transformation of As from As-bearing iron minerals under anaerobic conditions, thus providing insights into the bioremediation of As-contaminated soil.

Thiosulfate driving bio-reduction mechanisms of scorodite in groundwater environment.

Reductive dissolution of scorodite results in the release and migration of arsenic (As) in groundwater. The purpose of this study was to explore the possible abiotic and biotic reduction of scorodite in groundwater environment and the effect of microbial-mediated sulfur cycling on the bio-reduction of scorodite. Microcosm experiments consisting of scorodite with bacterium Citrobacter sp. JH012-1 or free sulfide were carried out to determine the effects of thiosulfate on the mobilization of As/Fe. The results show arsenic release is positively correlated with iron reduction. The arsenate [As(V)] released can agglomerate with Fe(II) on the surface of scorodite to form crystalline parasymplesite, while no parasymplesite was detected in the abiotic reduction of scorodite by sulfide. The reduction of scorodite and As(V) was affected by thiosulfate. When 0.5 mM thiosulfate was added, the Fe(III) reduction rate increased from 32% to 82%, and the As(V) reduction rate rose from 54% to 64%. When the addition of thiosulfate was increased from 0.5 mM to 2 mM and 5 mM, Fe(III) reduction rate added 4% and 8%, and As(V) reduction rate increased 11% and 16%, respectively. In addition, the presence of thiosulfate promoted the scorodite almost completely converting to parasymplesite. Therefore, the effect of microbial-mediated sulfur cycling should be considered in arsenic migration and reduction from scorodite.

Utilization of Lead Slag as In Situ Iron Source for Arsenic Removal by Forming Iron Arsenate.

In situ treatment of acidic arsenic-containing wastewater from the non-ferrous metal smelting industry has been a great challenge for cleaner production in smelters. Scorodite and iron arsenate have been proved to be good arsenic-fixing minerals; thus, we used lead slag as an iron source to remove arsenic from wastewater by forming iron arsenate and scorodite. As the main contaminant in wastewater, As(III) was oxidized to As(V) by H2O2, which was further mineralized to low-crystalline iron arsenate by Fe(III) and Fe(II) released by lead slag (in situ generated). The calcium ions released from the dissolved lead slag combined with sulfate to form well-crystallized gypsum, which co-precipitated with iron arsenate and provided attachment sites for iron arsenate. In addition, a silicate colloid was generated from dissolved silicate minerals wrapped around the As-bearing precipitate particles, which reduced the arsenic-leaching toxicity. A 99.95% removal efficiency of arsenic with initial concentration of 6500 mg/L was reached when the solid-liquid ratio was 1:10 and after 12 h of reaction at room temperature. Moreover, the leaching toxicity of As-bearing precipitate was 3.36 mg/L (As) and 2.93 mg/L (Pb), lower than the leaching threshold (5 mg/L). This work can promote the joint treatment of slag and wastewater in smelters, which is conducive to the long-term development of resource utilization and clean production.

Removal of arsenic in acidic wastewater using Lead-Zinc smelting slag: From waste solid to As-stabilized mineral.

High-arsenic wastewater has long been considered a major threat to ecological balance and human health because of its strong toxicity and high mobility. Herein, an environmentally friendly process was proposed for As removal and fixation in the form of As-stabilized mineral, using Lead-Zinc smelting (LZS) slag as the in situ Fe donor, neutralizer, and crystal seed. The slag was dissolved in the wastewater and released Fe and Ca ions, while simultaneously increasing the pH value of the solution to help scorodite synthesis. The dissolved Ca2+ ion preferentially reacted with SO42- ion in the form of CaSO4·2H2O precipitate as in situ "seeds" for As precipitation. The dissolved Fe(II) and As(III) ions were oxidized to Fe(III) and As(V) ions by H2O2, and later reacted with each other to generated amorphous ferric arsenate on the surface of CaSO4·2H2O, and then evolved into scorodite crystals with high stability. With a Fe/As molar ratio of 2, a reaction temperature of 90 °C, and a reaction time of 12 h, 98.42% of As was effectively precipitated from the wastewater with an initial As concentration of 7530.00 mg/L. Moreover, the leached As concentration of the As-bearing precipitate in the TCLP test was 3.46 mg/L. The concentration of the residual As and heavy metals ions in the final filtrate was lower than local wastewater discharge standards, successfully realizing the treatment of smelting wastewater. In summary, a prospective process successfully shows a great potential for co-treatment of LZS wastewater and slag, which could advance the large-scale disposal of LZS plants.

Effects of Fe(II)-induced transformation of scorodite on arsenic solubility.

Scorodite (FeAsO4·2H2O) is a pivotal secondary ferric arsenate that immobilizes most of arsenic (As) in acidic As-contaminated environments, but secondary As pollution may occur during dissolution of scorodite in environments involving redox changes. Reductive dissolution of scorodite by coexisting dissolved Fe2+ (Fe(II)aq) under anaerobic conditions and its effects on the behavior of As have yet to be examined. Here, this study monitored the changes in mineralogy, solubility and speciation of As during scorodite transformation induced by Fe(II) under anaerobic conditions at pH 7.0 and discussed the underlying mechanisms. Mössbauer and X-ray diffraction (XRD) analysis showed the formation of parasymplesite and ferrihydrite-like species during scorodite transformation, which was highly controlled by Fe(II)aq concentrations. 1 mM Fe(II)aq enhanced As mobilization into the solution, whereas As was repartitioned to the PO43--extractable and HCl-extractable phases with 5 and 10 mM Fe(II). The neo-formed parasymplesite and ferrihydrite-like species immobilized dissolved As(V) through adsorption and incorporation. Additionally, As(V) reduction occurred during Fe(II)-induced scorodite transformation. Our results provide new insights into the stability and risk of scorodite in anaerobic environments as well as the geochemical behavior of As in response to Fe cycling.

Partitioning and transformation behavior of arsenic during Fe(III)-As(III)-As(V)-SO42- coprecipitation and subsequent aging process in acidic solutions: Implication for arsenic mobility and fixation.

The coprecipitation and subsequent aging of Fe(III)-As(III)-As(V)-SO42- play an important role in controlling As behavior in acidic systems, such as acid mine drainage and hydrometallurgical acid waste. In this study, we investigated the redistribution and transformation of As in the Fe(III)-As(III)-As(V)-SO42- system (As(III)/As(V) ≈ 1) at different Fe/As molar ratios (i.e., 0.25, 0.5, and 1) and pH (1.2 and 1.8) at 60 °C. The results showed that As(III) and SO42- can be incorporated into the amorphous ferric arsenate and scorodite host phases by forming a Fe(AsO4)x(AsO3)y(SO4)z solid solution. As(III) contents in the freshly coprecipitated solids increased with pH and initial As(III) concentrations. During aging process, As(III) contents in the solid products with Fe/As molar ratios of 0.5 and 1 increased with aging time at pH 1.8. In contrast, As(III) was gradually expelled from aging products with aging time at pH 1.2, regardless of Fe/As molar ratio. X-ray diffraction (XRD), scanning electron microscopy (SEM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and Raman spectroscopy characterization results showed that an As(III)-SO42--doped scorodite was formed at Fe/As molar ratio ≤0.5 during the aging process. It was also found that As(III) had an inhibitory effect on the transformation of poorly crystalline ferric arsenate to scorodite. The present study may have important implications for understanding the geochemical cycle of As, Fe, and SO42- in acidic solutions and give further understanding on the mechanisms involved in As removal and fixation in hydrometallurgical unit operations.

Arsenic removal procedure for the electrolyte from a hydro-pyrometallurgical complex.

Commercial copper (Cu) is obtained by a hydro-pyrometallurgical process, where the Cu anodes obtained in the furnaces (Cu > 99.5%) are enriched up to 99.99% in "cathodes" by electrorefining at an electrolysis plant. During this process, some impurities accumulate in the electrolyte, mainly arsenic (As), which decrease the quality of the Cu cathode. For this reason, the electrolyte is sent to an electrolyte cleaning plant (ECP) for its purification. Electrolyte sludge (ES) is produced in the last stage of purification and is recirculated back to the furnace due to the high Cu content. This recirculation involves a severe problem of As accumulation in the industrial process. The objective of this work was to develop a procedure to fully dissolve the ES, removing the As and recovering its Cu content. The ES dissolution process was optimised (dissolution efficiency > 99%) in H2SO4 (1.4 M)/HNO3 (1.8 M) medium using a 1:20 g mL-1 solid-to-liquid ratio. As was removed from the ES solution by its precipitation as iron (III) arsenate, with high efficiency (more than 70%). After As removal, the Cu can be precipitated as copper sulphate, which is used in several applications.

Hydrothermal treatment of arsenic sulfide slag to immobilize arsenic into scorodite and recycle sulfur.

Arsenic sulfide slag (ASS) is typically by-produced from arsenic-containing wastewater treatment. In this work, a novel hydrothermal treatment method with the assistance of Fe(NO3)3 (HT-Fe(NO3)3) was developed to detoxify ASS by transforming arsenic into scorodite and extracting sulfur in one step. After hydrothermal treatment, As(III) in ASS was oxidized and immobilized into the stable scorodite with a high As immobilization efficiency (~99%), and the toxicity leachability of arsenic-containing solid waste significantly reduced from 634.2 to 2.5 mg/L, well below the discharge standard of solid waste. Further study reveals that the nucleation and growth process was fit well by Avrami-Erofeev model and followed Ostwald step rule, which involved the As2S3 dissolution, formation of amorphous ferric arsenate and then crystallization within the amorphous precursor. In this process, sulfur originated from As2S3 played an important role by serving as the heterogeneous nuclei to decrease the barrier for the formation of amorphous ferric arsenate, and facilitated the transformation of as-formed scorodite from nano-sheet aggregates to the bulk and dense spherical polymorph, which further increased the stability of the arsenic contained solid product. This study will shed light on the development of new technologies for treatment of industrial solid waste and recycle of useful resources.

Acid mine drainage formation and arsenic mobility under strongly acidic conditions: Importance of soluble phases, iron oxyhydroxides/oxides and nature of oxidation layer on pyrite.

Acid mine drainage (AMD) formation and toxic arsenic (As) pollution are serious environmental problems encountered worldwide. In this study, we investigated the crucial roles played by common secondary mineral phases formed during the natural weathering of pyrite-bearing wastes-soluble salts (melanterite, FeSO4·7H2O) and metal oxides (hematite, Fe2O3)-on AMD formation and As mobility under acidic conditions (pH 1.5-4) prevalent in historic tailings storage facilities, pyrite-bearing rock dumps and AMD-contaminated soils and sediments. Our results using a pyrite-rich natural geological material containing arsenopyrite (FeAsS) showed that melanterite and hematite both directly-by supplying H+ and/or oxidants (Fe3+)-and indirectly-via changes in the nature of oxidation layer formed on pyrite-influenced pyrite oxidation dynamics. Based on SEM-EDS, DRIFT spectroscopy and XPS results, the oxidation layer on pyrite was mainly composed of ferric arsenate and K-Jarosite when melanterite was abundant with/without hematite but changed to Fe-oxyhydroxide/oxide and scorodite when melanterite was low and hematite was present. This study also observed the formation of a mechanically 'strong' coating on pyrite that suppressed the mineral's oxidation. Finally, As mobility under acidic conditions was limited by its precipitation as ferric arsenate, scorodite, or a Fe/Al arsenate phase, including its strong adsorption to Fe-oxyhydroxides/oxides.

The effect of precursor speciation on the growth of scorodite in an atmospheric scorodite synthesis.

In this study, we propose a growth pathway of scorodite in an atmospheric scorodite synthesis. Scorodite is a non-direct product, which is derived from the transformation of its precursor. Different precursor speciation leads to different crystallinity and morphology of synthesized scorodite. At 10 and 20 g l-1 initial arsenic concentration, the precursor of scorodite is identified as ferrihydrite. At 10 g l-1 initial arsenic concentration, low arsenic concentration is unfavourable to the complex between arsenate and ferrihydrite, inhibiting the transformation of ferrihydrite into scorodite. The synthesized scorodite is 1-3 µm in size. At 20 g l-1 initial arsenic concentration, higher arsenic concentration favours the complex between arsenate and ferrihydrite. The transformation process is accessible. Large scorodite in the particle size of 5-20 µm with excellent crystallinity is obtained. However, the increasing initial arsenic concentration is not always a positive force for the growth of scorodite. When initial arsenic concentration increases to 30 g l-1, Fe(O,OH)6 octahedron preferentially connects to As(O,OH)4 tetrahedron to form Fe H 2 As O 4 2 + or FeHAs O 4 + ion. Fe-As complex ions accumulate in solution. Once the supersaturation exceeds the critical value, the Fe-As complex ions deprotonate and form poorly crystalline ferric arsenate. Even poorly crystalline ferric arsenate can also transform to crystalline scorodite, its transformation process is much slower than ferrihydrite. Therefore, incomplete developed scorodite with poor crystallinity is obtained.

Bioremediation of highly toxic arsenic via carbon-fiber-assisted indirect As(III) oxidation by moderately-thermophilic, acidophilic Fe-oxidizing bacteria.

OBJECTIVE: To enable removal of highly toxic As(III) from acidic waters by inducing indirect microbial As(III) oxidation by Fe-oxidizing bacteria via carbon-assisted redox-coupling between As(III) oxidation and Fe3+ reduction. RESULTS: Carbon-fiber (CF) was shown to function as an electron-mediator to catalyze chemical (abiotic) redox-coupling between As(III) oxidation and Fe3+ reduction. Accordingly, by taking advantage of Fe3+ regeneration by Fe-oxidizing bacteria, it was possible to promote oxidative removal of As(III) as ferric arsenate at moderate temperature. This reaction can be of use under the situation where a high-temperature treatment is not immediately available. Arsenic once concentrated as ferric arsenate on carbon-fibers can be collected to undergo phase-transformation to crystalline scorodite as the next re-solubilization/re-crystallization step at a higher temperature (70 °C). CONCLUSIONS: While extremely acidophilic Fe-oxidizing bacteria are widely found in nature, the As-oxidizing counterparts, especially those grown on moderately-thermophilic and mesophilic temperatures, are hardly known. In this regard, the finding of this study could make a possible introduction of the semi-passive, low-temperature As-treatment using readily available Fe-oxidizing bacteria.

The Synthesis of the Pomegranate-Shaped α-Fe2O3 Using an In Situ Corrosion Method of Scorodite and Its Gas-Sensitive Property.

The release of hazardous gas increases with the development of industry. The research of gas-sensitive materials has attracted attention. Nanoscale iron oxide (α-Fe2O3) is one of the research hotspots of gas-sensitive materials because it is a cheap, non-toxic semiconductor material. In this study, pomegranate-shaped α-Fe2O3 was synthesized using an in situ corrosion method of scorodite. Spherical-shaped α-Fe2O3 nanoparticles were included in the octahedral shells. The forming process of the structure was analyzed by a variety of measurements. The shell was formed first through the deposition of Fe(OH)3, which was produced by hydrolyzing scorodite. Then, the corrosion was continued and Fe(OH)3 precipitation was produced below the shell. The particles aggregated and formed spheres. The pomegranate-shaped α-Fe2O3 was formed when the scorodite was hydrolyzed completely. The gas-sensing properties of α-Fe2O3 were investigated. The results showed that pomegranate-shaped α-Fe2O3 was responsive to a variety of gases, especially xylene. The value of Ra/Rg was 67.29 at 340 °C when the concentration of xylene was 1000 ppm. This indicated the pomegranate-shaped α-Fe2O3 has potential application as a xylene gas sensor.

Hematite-catalysed scorodite formation as a novel arsenic immobilisation strategy under ambient conditions.

Scorodite is an important mineral not only for arsenic (As) removal from industrial wastewaters but also in the mobility and final fate of As in waste rocks, contaminated soils and sediments, and mine tailings. Because of the mineral's high As-loading capacity and stability, numerous studies have been done to understand its formation. Unfortunately, most of these studies were limited to elevated temperatures (>70 °C), so the processes involved in scorodite formation under ambient conditions remain unclear. This study provides evidence of the catalytic effects of hematite on the formation of scorodite at 25 °C in a pyrite-rich natural geologic material. Scorodite peaks were detected in the XRD patterns of the leaching residues with and without hematite, but those in the former were stronger and more pronounced than the latter. These results suggest that the formation of scorodite was catalysed by hematite, a generalisation that is further supported by strong characteristic IR absorption bands of scorodite at 819 cm-1 (As-O bending vibration), 785 and 725 cm-1 (As-O stretching vibrations), and 2990 cm-1 (OH-vibration) as well as the distinct XPS binding energies of Fe(III)-As (709.7 eV), As(V)-O (44.8, 44.31 and 43.7 eV), O2- (530.5 eV) and coordinated water (531.3 eV) in scorodite. This phenomenon could be attributed to three possible mechanisms: (1) more rapid precipitation promoted by the "seeding" effect of hematite particles, (2) additional supply of Fe3+ from hematite dissolution under acidic conditions, and (3) enhanced oxidations of Fe2+ to Fe3+ and As(III) to As(V) on the surface of hematite.

Self-enhanced and efficient removal of arsenic from waste acid using magnetite as an in situ iron donator.

High arsenic-containing waste acid from the heavy nonferrous metallurgical sector (Cu, Pb, Zn, Ni, Sn, etc.), one of the most dangerous arsenic hazardous wastes with extremely high arsenic concentrations, has presented enormous challenges to the environment and caused severe environmental pollution over the past few decades due to the lack of affordable and environmentally friendly disposal technologies. Here, we report a green process for the self-enhanced and efficient removal of arsenic from waste acid using magnetite as an in situ iron donator. Firstly, the room-temperature predissolution of magnetite in waste acid provides initial iron ions as a starting precipitator of arsenic, simultaneously providing a suitable pH range and an active surface that are ready for the nucleation and growth of scorodite. Afterwards, arsenic is precipitated in form the of scorodite, which is driven by a mutually improved cycle composed of arsenic precipitation and magnetite dissolution on the surface of magnetite particles. This cycle creates a low supersaturation of iron and constant pH in the waste acid, ensuring the continuous precipitation of arsenic as well-crystallized and environmentally stable scorodite by using magnetite as an in situ iron donator via the reaction of 2Fe3O4 + 6H3AsO4 + H2O2 = 6FeAsO4 + 10H2O. Under optimal conditions, including a 6-h room-temperature predissolution, a 12-h atmospheric reaction at 90 °C and a pH of 2.0 with a magnetite dosage at the Fe3O4/As molar ratio (the molar ratio of Fe3O4 in magnetite to As in waste acid) of 1.33, 99.90% of arsenic was successively removed from waste acid with an initial arsenic concentration of 10300 mg/L. In combination with the good adaptability of this process, the performed case study and prospective process show the successful removal of arsenic from waste acid as well as great potential for large-scale applications.

Immobilization of arsenic as scorodite by a thermoacidophilic mixed culture via As(III)-catalyzed oxidation with activated carbon.

In this study we describe the immobilization of arsenic as scorodite (FeAsO4.2H2O) by a thermophilic iron-oxidizing mixed culture from an acidic sulfate medium containing 500 mg L-1 of Fe(II), 500 mg L-1 As(III) and granular activated carbon (GAC) as the main arsenite oxidant. This study shows that crystalline scorodite can only be precipitated in the presence of the ferrous iron-oxidizing mixed culture (pH 1.3 and 70 °C). The efficiency of arsenite oxidation was over 99% with a maximum specific oxidation rate of 280 mgAs(III) gGAC-1 day-1. Ferrous iron and arsenite were also oxidized in the absence of the mixed culture, however, no scorodite precipitated under these conditions; consequently, scorodite precipitation was biologically induced. The precipitated scorodite particles had a size between 0.5 and 10 µm with an average of 5 µm, resulting in low settling rates. Ion activity product calculations and observations by Scanning Electron Microscopy (SEM) indicated that microbial cells served as surface for heterogeneous nucleation. The potential of the thermophilic mixed culture for the scorodite formation explored in this study provides the basis of a new approach for the treatment of As(III) polluted streams.