Arsenic Fixation Research Articles

Effect of seawater and dissolved cations on scorodite synthesis via iron coprecipitation

In recent years, one of the more effective developments in the fixation of arsenic from nonferrous waste has been the synthesis of scorodite via the co-precipitation of arsenic with iron during Fe(II) oxidation. This work examines the impact of cation impurities on the process with the aim of widening the application of this approach to incorporate the use of seawater and the treatment of ferrous metallurgy waste. Scorodite formation was promoted by the presence of cations in the order of Cu2+ >> Zn2+ > Al3+ > Ca2+ ∼ Mg2+, with differences in precipitation behaviour, yield and kinetics due to specific cation effects on iron oxidation. A grain size increase was observed with Cu, while the opposite was found with Al, attributed to crystallisation from solution over epitaxial growth. The use of seawater decreased As precipitation by <4 % without affecting grain size, showing the potential to be utilised as reaction medium. While the presence of Na+ hinders As precipitation, the impact appears less pronounced with seawater due to competing effects from other cations. Since scorodite precipitation is slowed down by high Fe(III) in the feed, a pre-reduction approach with Al, Cu and Zn base metals was examined for conversion of Fe(III) in metallurgical waste to Fe(II) prior to co-precipitation with As. While this produced stable scorodite precipitates, the yield and presence of unstable by-products were impacted by the method of reductant addition.

Scorodite synthesis process using solid iron oxides

The immobilization of arsenic in the form of scorodite (FeAsO4·2H2O), which has excellent chemical stability, is attracting attention as a method for treating wastewater containing high concentrations of arsenic generated at nonferrous metal smelting plants. Scorodite, with its low solubility and high arsenic content per volume, is expected to be an environmentally friendly arsenic fixation method suitable for final disposal. Various scorodite synthesis methods have been studied. The first synthesis method proposed is the hydrothermal method using an autoclave to synthesize highly crystalline scorodite. Although the hydrothermal method is capable of synthesizing scorodite with good crystallinity, from an economic point of view, scorodite synthesis under ambient pressure and at low temperatures is more attractive. As a low-temperature scorodite synthesis method under atmospheric pressure, the oxidation of Fe(II) process by O2 bubbling was proposed. In this method, ferrous sulfate is added to an arsenic-containing solution as a Fe ion source, and in situ oxidation of Fe(II) by O2 or air bubbling to form scorodite with good crystallinity. In addition to temperature, other conditions, pH, Fe/As ratio, and reaction time have been reported to affect scorodite crystallization. Recently, scorodite synthesis using solid iron oxide as the Fe source for scorodite synthesis, instead of aqueous Fe salt solutions, has attracted much attention. In this presentation, we will report on the investigation of reaction parameters, such as the type of iron oxide and reaction temperature, for the scorodite synthesis using solid iron oxide.

Characterisation of arsenic levels in acid-treated arsenic-containing sludge after steel slag-fly ash gel curing

ABSTRACT Arsenic-containing sludge (ABG) is a common hazardous waste in the metallurgical industry and poses a serious threat to environmental safety. However, its instability and mobility have a significant impact on the environment. Traditional curing methods are time-consuming and costly, often resulting in incomplete curing. In this study, we introduce a curing/stabilisation method with a steel slag-fly ash gel material after ABG acid treatment. The toxic leaching of arsenic from ABG was reduced to 220 mg/kg by treating the sludge with acids (H2SO4-H3PO4) at different solid-to-liquid ratios. Afterward, H2O2 was added to oxidise As(III) to As(V). The ABG was cured/stabilised using an alkali-activated steel slag-fly ash gel material. The cured product exhibited optimal arsenic fixation under an ABG/steel slag/fly ash mass ratio of 1:4:2, a curing temperature of 60°C, a curing time of 20 h, and an ambient pH of 12.5. Under these conditions, steel slag-fly ash facilitated Ca-As precipitation, resulting in a hydration reaction that produced C-S-H gel. Additionally, the reaction generated calcium hydroxide, calcium and iron pyroxene, silica, and iron ferrite, which adsorbed part of the free arsenic, completing the curing of the acid-treated ABG and stabilising arsenic leaching toxicity. The leaching of arsenic in the ABG was much lower than the Chinese ‘Hazardous Wastes Leaching Toxicity Identification Standard’ (GB5085.3-2007) (5 mg/L), with an arsenic curing rate exceeding 99%. The mechanism of arsenic solidification involves the combined effects of chemical precipitation, physical encapsulation, and adsorption. Collectively, our findings demonstrated that the use of steel slag-fly ash gel as a functional material for ABG curing holds considerable environmental and economic benefits. Therefore, this study provides theoretical guidance and provides insights into the experimental feasibility of ABG treatment.

Cotreatment strategy for hazardous arsenic-calcium residue and siderite tailings via arsenic fixation as scorodite

Siderite tailings is a potentially cost-free iron (Fe) source for arsenic (As) fixation in hazardous arsenic-calcium residues (ACR) as stable scorodite. In this study, a pure siderite reagent was employed to investigate the mechanism and optimal conditions for As fixation in ACR via scorodite formation, while the waste siderite tailings were used to further demonstrate the cotreatment method. The cotreatment method starts with an introduction of sulfuric acid to the ACR for As extraction and gypsum precipitation, and is followed by the addition of H2O2 to oxidize As(III) in the extraction solutions and finalized by adding siderite with continuous air injection for scorodite formation. The dissolution-oxidation of siderite can slowly produce Fe(III) to control aqueous As(V)-Fe(III) precipitation supersaturation for continuous scorodite crystallization. Chemical analyses show that the extraction efficiency of As from the ACR reaches 94.55%, while the precipitation yield of extracted As via scorodite formation arrives at 99.63% and 99.47%, leading to fixation efficiency of 94.20% and 94.04% in terms of the total As in the ACR by using siderite reagent and tailings, respectively. The final solid products show desirable TCLP stability and long-term stability, meeting the requirement for safe storage (GB 5085.3–2007). XRD, FTIR, and TEM results reveal that such high stability is attributable to the formation of scorodite and the surface adsorption of As on the raw siderite and secondary maghemite. This innovative and economical application of siderite tailings for the treatment of hazardous ACR can be extended to the management of hydrometallurgical wastes.

A Study on the Soil Passivation of Nano-Manganese Dioxide-Modified Biochar under High-Arsenic Water Irrigation

[Objective] The irrigation area in northern Henan is an important grain producing area in China. Native high arsenic groundwater exists in the area and has long been used for agricultural irrigation. Increased soil arsenic (As) content under long-term irrigation threatens the quality and safety of crop products. Soil passivation is the use of adding passivators to the soil to fix pollutants to achieve the purpose of limiting their migration. Therefore, the preparation of an efficient and clean passivator and its arsenic fixation effect in soil are important research areas to reduce the risk of high arsenic groundwater. [Method] Firstly, nano-manganese dioxide (MnO2)-modified biochar was prepared via the pyrolysis of sawdust biochar, potassium permanganate and manganese sulfate monohydrate at a mass ratio of 1:0.18:0.29. Secondly, the adsorption characteristics were explored using adsorption kinetics and adsorption isothermal experiments. Scanning electron microscopy (SEM), X-ray powder diffraction (XRD) feature mapping and other characterization methods were used to study its physical properties and adsorption mechanism. Finally, a potting experiment was designed to explore the changes in arsenic content in soil when the passivator dosages were 0%, 1% and 5%. [Results] (1) The nano-MnO2 modified biochar could reach the adsorption dynamic equilibrium after 180 min, and its maximum adsorption capacity was 58.12 μg/g. (2) When the dosing ratio was 1%, the fixed efficiency of soil effective As content in potted crops of unplanted crops and planted crops was 4.18–5.51% and 1.99–3.83%. When the dosing ratio was 5%, it was 7.48–8.75% and 5.58–9.58%. [Conclusions] The results show that when the addition ratio is 0–5%, the passivation effect of soil effective As is positively correlated with the passivator dosage.

The effects of arsenic trioxide addition on the mechanical and geochemical properties of the cemented paste backfill

Cemented paste backfill (CPB) technology, a densified mixture of mine tailings, binding material, and water, thickens to form a non-settling paste that is transported to fill mined cavities. CPB could provide environmental advantages by preventing the release of contaminants through hydraulic binder stabilization/solidification. Up to now, only few studies have been carried out to examine the feasibility of arsenic (As) fixation within cemented paste backfills. The main objective of the current study is to assess the impacts of incorporating pure arsenic trioxide on the geomechanical and geochemical properties of cemented paste backfill. CPB samples were prepared using pure ground silica (Sil-Co-Sil®) mimicking mine tailings, general use (GU) cement, deionized water, and reagent-grade pure As2O3 at different arsenic contents (0, 5, 10, and 15%). The samples were cured for up to 28 days and unconfined compressive strength (UCS) tests were conducted after 7 and 28 days of curing. Moreover, to evaluate the geochemical behavior of the pastes, mixtures of GU cement, pure As2O3 (0–15%), and deionized water with the same proportions as the CPB samples were prepared and mixed for up to 28 days. Then, pH, EC and chemical composition of the mixtures were evaluated. Results showed that the addition of pure arsenic trioxide (as a partial substitution for pure silica) leads to a substantial decrease in the mechanical strength of the CPB samples. However, this adverse effect was more substantial for the arsenic content of 5 wt%. The strength of the As2O3-containing samples did not improve significantly after 7 days of curing and arsenic addition lowered the pH of the solutions Microstructural analysis using SEM proved the formation of some C–S–H gels that contained arsenic in their structures as well as some complex mixture of oxides for the case of the As2O3-cement mixtures.

Electrochemical investigation of scorodite synthesis for arsenic fixation using hematite as an iron source: Elucidation of reaction acceleration by Fe2+ using a local-cell model

Owing to the chemical stability of scorodite, the synthesis of scorodite for arsenic fixation has gained interest as a treatment method for arsenic-containing wastewater generated at nonferrous metal smelting plants and other facilities. Diverse synthesis processes have been investigated such as hydrothermal, oxidation, and solid iron oxide methods. The solid iron oxide method using hematite as an iron source is particularly promising owing to its many advantages. Though the overall reaction equation for this process does not include Fe2+, the reaction is influenced by Fe2+ in the solution, significantly increasing the reaction rate. In the present study, we examine the mechanism of this reaction electrochemically to elucidate the role of Fe2+. By analyzing the open-circuit potentials and the polarization behaviors of each local reaction and conducting short-circuiting experiments based on the predicted local-cell model, we demonstrate the electrochemical nature of the reaction, which involves the reduction of hematite and the oxidation of Fe2+. In addition, the multistep reaction involved in the formation of scorodite is discussed using potential–pH diagrams based on thermodynamic reference data.

Arsenic Fixation by Aged Ferrihydrite Nanoparticles.

Arsenic Fixation by Aged Ferrihydrite Nanoparticles.

The adsorption mechanism of arsenic in flue gas over the P-doped carbonaceous adsorbent: Experimental and theoretical study

The utilization of carbon-based sorbent has gained extensive attention for arsenic removal from flue gas due to their high specific surface area, sufficient active sites and abundant sources. This study proposes that the addition of phosphorous could be used as an effective promoter for the activation and modification of carbonaceous sorbent to enhance their arsenic fixation capacity. Both experimental and density functional theory (DFT) methods were employed to systematically investigate the adsorption characteristics of arsenic over different carbon based sorbents. The results reveal that the modification of H3PO4 generated C-O-P, C-P-O, and C3-P-O functional groups on the surface of activated carbon, and the adsorption ability of H3PO4-modified activated carbon for gaseous arsenic was significantly improved compared with the untreated activated carbon. DFT calculations indicate that unsaturated C atoms on carbonaceous surface served as active sites during arsenic adsorption, the electronegativity of which could be enhanced by phosphorous functional group, thereby facilitating the adsorption of gaseous arsenic species. Additionally, the positive effect of the phosphorous functional group on arsenic adsorption is more pronounced on zigzag carbonaceous surface than on armchair carbonaceous surface. This work provides a theoretical basis of the development of high-performance biochar preparation for arsenic adsorption by explaining the promoting effect of phosphorous functional group on gaseous arsenic adsorption on carbonaceous surface.

First principles study of structural and electron properties in scorodite: the bulk and surface.

Scorodite (FeAsO4·2H2O) is an ideal material for the fixation of arsenic that has attracted considerable research interest in recent decades. However, the position of the H atom in the scorodite crystal structure, water molecular configuration, surface morphology, and chemical state of the surface atoms have not been reported. In this work, density functional theory (DFT) is used to optimize the scorodite crystal structure, and the atomic bonding is analyzed. At the same time, a surface model is constructed to calculate the configuration and electronic structure of the surface atoms for different coordination groups. The results show that the tetrahedral [AsO4] and octahedral [FeO4(2H2O)] groups in the scorodite crystal structure have good stability(geometry configuration), and the covalent bond strength between the As atom and the bridged oxygen atom (Ob) is greater than that between the Ob atom and the Fe atom. The water molecules in the crystal structure do not seriously deform and ionize. The configuration of the water molecules remains stable through electrostatic interactions (Ow-Fe) and hydrogen bonding (H-Ob). The Fe atoms on the surface of scorodite can coordinate with OH and H2O, while the As atoms can only form a stable coordination with OH. When an Fe atom on the surface coordinates with two H2O atoms, the Fe atom will shrink to the inside of the bulk. With the increase in the hydroxylation number of the Fe atom, the bonding strength between the Fe atom and the Ob atom decreases. Different surface configurations do not affect the stability(geometry configuration) of the [AsO4] structure. In addition, the surface water molecular layer has a very weak effect on the surface coordination configuration. By contrast, in the surface configuration of the (W + OH) structure, the change in the surface atomic layer spacing is the smallest.

Distribution behavior and deportation of arsenic in copper top-blown smelting process

In recent years, the impurity content in copper concentrate increases gradually with the consumption of high-grade copper ore. When the arsenic content in the raw materials increases, large amounts of arsenic enter the sulfuric acid system, resulting in large amounts of waste acid that put great pressure on production and environmental protection. Using the distribution characteristics of arsenic in each phase, the possibility of enriching arsenic in the form of stable arsenates in the slag was investigated to enrich arsenic in the form of stable arsenates in the slag. It is shown that increasing CaO content in slag at relatively low temperatures, controlling the slag type and changing the slag composition effectively improved the ability of the slag to absorb arsenic. Based on a theoretical analysis used to optimize the process parameters and determine a reasonable slag type, an oxygen-enriched top-blown smelting experiment was conducted with mixed copper concentrates. The mechanism of arsenic fixation in smelting slag at a smelting temperature of 1180 °C (1453 K) was investigated, and the results showed that the As content in slag was increased by 20∼50% and decreased by 10∼30% and 10∼20% in the dust and matte, respectively. Thus, arsenic is fixed in silicate in the form of stable arsenate, which can be an effective and safe treatment solution for copper smelting processes.

Synergy of directional oxidation and vacuum gasification for green recovery of As2O3 from arsenic-containing hazardous secondary resources

Arsenic, a hazardous material that is toxic for humans, enters the human body through soil, water, and air. Furthermore, metal smelting is known to produce arsenic-containing hazardous secondary resources (AHSRs), which cause irreversible damage to the total environment. Therefore, a novel, clean, and efficient arsenic fixation technology has been developed in this study for arsenic removal, which involves directional oxidation and vacuum gasification of AHSRs. Oxidation results revealed that physical phases containing arsenic (As, As2O3, As2Te3 and Cu3As) are selectively oxidized to As2O3 completely and thus classified as oxidative modulation products (OMPs). Meanwhile, approximately 98.82% As2O3 of OMPs convert into volatiles in the following gasification. Characterization results showed that As2O3 with 96.72% purity and uniform microscopic distribution was obtained in the form of monoclinic crystalline needle-like crystals. The proposed approach organically combines oxidation and volatilization properties of each element to facilitate clean and efficient separation as well as recovery of As2O3. No hazardous gas or wastewater is discharged during the entire process, thereby ensuring that arsenic is recycled in a sustainable and clean manner. Overall, this study provides a clean and low-carbon approach for recycling secondary resources containing arsenic.

Mechanism and Environmental Effect on Nitrogen Addition to Microbial Process of Arsenic Immobilization in Flooding Paddy Soils

China is one of the largest rice producers in the world, and rice production plays an important role in food security. Currently, arsenic pollution in paddy soils is one of most serious soil pollutions in China. Since paddy soils are maintained in a flooding anoxic condition for long periods, the rate and extent of arsenic transformation processes governed by microbial activities are stronger than that of chemical processes. Thus, understanding the key processes and relating mechanisms of microbial arsenic fixation in paddy soils will provide a theoretical basis for controlling arsenic pollution in paddy soils. In this study, based on a comprehensive analysis of arsenic migration in paddy soils and relating influencing factors, two important pathways relating to As(Ⅲ) fixation through microbial activities were illustrated:microbial ČFe(Ⅱ) oxidation coupled with As(Ⅲ) fixation (indirect process) and direct fixation through microbial As(Ⅲ) oxidation (direct process). Additionally, the influences of speciation and the distribution of nitrogen in paddy soils to the processes of microbial arsenic fixations were discussed and by extension, the expressions of key genes and metabolic mechanisms relating to microbial arsenic fixation and nitrogen transformation. Finally, the recent advances in microbial remediation used to control arsenic pollution in paddy soils were summarized, and relating future perspectives targeting microbial remediation were proposed.

Optimization of Arsenic Fixation in the Pressure Oxidation of Arsenopyrite Using Response Surface Methodology

ABSTRACT Arsenic is a common pollutant and impurity present in complex gold ores. In the pressure oxidation (POX) of refractory gold-bearing sulfides, a major environmental challenge is the treatment of the hazardous waste released from arsenic-bearing minerals during processing. While the bulk removal of arsenic from solution can occur during POX, the formation of stable arsenates relies on the operating conditions during POX and the subsequent curing stage. Herein, response surface methodology (RSM) and central composite design have been investigated as viable approaches for optimizing arsenic fixation during the curing of the POX product of arsenopyrite. Curing time (0–24 h) and temperature (60–120°C) were examined as the model variables for RSM optimization, and the performance was assessed via arsenic and iron precipitation, along with the change in free acid and sulfate concentrations. Experimental validation of the optimized model conditions demonstrated good agreement with the simulated outputs and provided a 10% increase in arsenic removal over the best model input. The formation of basic ferric arsenate sulfate and scorodite under these conditions was supported by RSM and confirmed via characterization. In the investigated system, the maximum arsenic removal occurs at a critical threshold temperature of 107°C, over which the scorodite formation decreases with temperature. Thermodynamic modeling revealed the preferable formation of soluble FeHAsO4 + complexes over scorodite above this threshold temperature, decreasing arsenic fixation at higher temperatures.

Methylocystis silviterrae sp.nov., a high-affinity methanotrophic bacterium isolated from the boreal forest soil.

A novel species is proposed for a high-affinity methanotrophic representative of the genus Methylocystis. Strain FST was isolated from a weakly acidic (pH 5.3) mixed forest soil of the southern Moscow area. Cells of FST are aerobic, Gram-negative, non-motile, curved coccoids or short rods that contain an intracytoplasmic membrane system typical of type-II methanotrophs. Only methane and methanol are used as carbon sources. FST grew at a temperature range of 4-37 °C (optimum 25-30 °C) and a pH range of 4.5 to 7.5 (optimum pH 6.0-6.5). The major fatty acids were C18 : 1ω8c, C18 : 1ω7c and C18 : 0; the major quinone as Q-8. FST displays 16S rRNA gene sequences similarity to other taxonomically recognized members of the genus Methylocystis, with Methylocystis hirsuta CSC1T (99.6 % similarity) and Methylocystis rosea SV97T (99.3 % similarity) as its closest relatives. The genome comprises 3.85 Mbp and has a DNA G+C content of 62.6 mol%. Genomic analyses and DNA-DNA relatedness with genome-sequenced members of the genus Methylocystis demonstrated that FST could be separated from its closest relatives. FST possesses two particulate methane monooxygenases (pMMO): low-affinity pMMO1 and high-affinity pMMO2. In laboratory experiments, it was demonstrated that FST might oxidize methane at atmospheric concentration. The genome contained various genes for nitrogen fixation, polyhydroxybutyrate synthesis, antibiotic resistance and detoxification of arsenic, cyanide and mercury. On the basis of genotypic, phenotypic and chemotaxonomic characteristics, it is proposed that the isolate represents a novel species, Methylocystis silviterrae sp. nov. The type strain is FST (=KCTC 82935T=VKM B-3535T).

Spectroscopic study on the local structure of sulfate (SO42−) incorporated in scorodite (FeAsO4·2H2O) lattice: Implications for understanding the Fe(III)-As(V)-SO42−-bearing minerals formation

AbstractThe incorporation of sulfate (SO42−) into the scorodite (FeAsO4·2H2O) lattice is an important mechanism during arsenic (As) fixation in natural and engineered settings. However, spectroscopic evidence of SO42− speciation and local structure in scorodite lattice is still lacking. In this study, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), sulfur K-edge X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopic analyses in combination with density functional theory (DFT) calculations were used to determine the local coordination environment of SO42− in the naturally and hydrothermally synthesized scorodite. The SO42− retention in natural scorodite and the effect of pH value and initial Na+ concentration on the incorporation of SO42− in synthetic scorodite were investigated. The results showed that trace amounts of SO42− were incorporated in natural scorodite samples. Scanning electron microscopy (SEM) results revealed that SO42− was homogeneously distributed inside the natural and synthetic scorodite particles, and its content in the synthetic scorodite increased slightly with the initial Na+ concentration at pH of 1.2 and 1.8. The FTIR features and XANES results indicated that the coordination number (CN) of FeO6 octahedra around SO42− in scorodite lattice is four. The DFT calculation optimized interatomic distances of S-O were 1.45, 1.46, 1.48, and 1.48 Å with an average of ~1.47 Å, and the interatomic distances of S-Fe were 3.29, 3.29, 3.33, and 3.41 Å with an average of ~3.33 Å. EXAFS analysis gave an average S-O bond length of 1.47(1) and S-Fe bond length of 3.33(1) Å with a CNS-Fe = 4 for SO42− in the scorodite structure, in good agreement with the DFT optimized structure. The results conclusively showed that SO42− in the scorodite lattice may be in the form of a Fe2(SO4)3-like local structure. The present study is significant for understanding the formation mechanism of scorodite in natural environments and hydrometallurgical unit operations for waste sulfuric acid treatment.

Dissolution, Solubility, and Stability of the Basic Ferric Sulfate-Arsenates [Fe(SO4)x(AsO4)y(OH)z·nH2O] at 25–45°C and pH 2–10

Basic ferric sulfate-arsenates [FeSAsOH, Fe(SO4)x(AsO4)y(OH)z·nH2O] were prepared and characterized to study their potential fixation of arsenic in the oxidizing and acidic environment through a dissolution for 330d. The synthetic solids were well-shaped monoclinic prismatic crystals. For the dissolution of the sample FeSAsOH–1 [Fe(SO4)0.27(AsO4)0.73 (OH)0.27·0.26H2O] at 25–45°C and initial pH 2, all constituents preferred to be dissolved in the order of AsO43− &gt; SO42− &gt; Fe3+ in 1–3 h, in the order of SO42− &gt; AsO43− &gt; Fe3+ from 1–3 h to 12–24 h, and finally in the order of SO42− &gt; Fe3+ &gt; AsO43−. The released iron, sulfate, and arsenate existed dominantly as Fe3+/Fe(OH)2+/FeSO4+, HSO4−/SO42−/FeSO4+, and H3AsO40/H2AsO4−, respectively. The higher initial pHs (6 and 10) could obviously inhibit the release of Fe3+ from solid into solution, and the solid components were released in the order of SO42− &gt; AsO43− &gt; Fe3+. The crystal tops were first dissolved, and the crystal surfaces were gradually smoothed/rounded until all edges and corners disappeared. The dissociations were restricted by the Fe-O(H) breakdown in the FeO6 octahedra and obstructed by the OH− and AsO4 tetrahedra outliers; the lowest concentration of the dissolved arsenic was 0.045 mg/L. Based on the dissolution experiment at 25°C and pH 2, the solubility products (Ksp) for the basic ferric sulfate-arsenate [Fe(SO4)0.27(AsO4)0.73 (OH)0.27·0.26H2O], which are equal to the ion activity products (logˍIAP) at equilibrium, were calculated to be -23.04 ± 0.01 with the resulting Gibbs free energies of formation (ΔGfo) of −914.06 ± 0.03 kJ/mol.

Separation and stabilization of arsenic in copper smelting wastewater by zinc slag

Copper smelting wastewater shows strong acidity, has a high arsenic concentration and has many types of heavy metals, which not only restricts the sustainable development of copper smelting enterprises but also poses a danger to the ecological environment. Here, we propose a new process for treating copper smelting wastewater with zinc slag. We studied both the solid-liquid chemical reaction process as well as the mechanism by which zinc slag removes arsenic in copper smelting wastewater in a water bath at 85 °C under atmospheric pressure. Specifically, 5 g of zinc slag reacted with copper smelting wastewater with an initial arsenic concentration of 6000 mg/L for 4 h resulted in an arsenic removal rate of 99.65%, and the leaching concentration of arsenic in the toxicity characteristic leaching procedure experiment was only 0.52 mg/L. Zinc slag is dissolved in Copper smelting wastewater to release iron ions and silicate. The solid-liquid reaction of the two is accompanied by coprecipitation of iron arsenate and the in-situ covering of silica gel, resulting in a core-shell precipitate with iron arsenate as the core and silica gel as the shell. The colloidal chemistry of silica gel and cations and its chemical stability can effectively prevent the dissolution of arsenic ions and significantly improve the stability of iron arsenate. Zinc slag, a dual functional material for removing arsenic and fixing arsenic, shows extraordinary potential for the removal and fixation of arsenic in copper smelting wastewater. This approach could further improve wastewater treatment in the non-ferrous smelting industry.

High arsenic levels in sediments, Jianghan Plain, central China: Vertical distribution and characteristics of arsenic species, dissolved organic matter, and microbial community

Elevated arsenic (As) levels in groundwater pose a risk to the local population that relies on this resource for their living needs. Here we analyzed samples collected from a sediment core recovered from Jianghan Plain, China, a region experiencing high As concentrations in groundwater. We evaluated the vertical distribution of As forms, fluorescent dissolved organic matter (DOM), microbial assemblages, and a suite of anions and cations. Our aim was to elucidate the As species in the local groundwater and their migration and transformation in the aquifer. As(III), Fe, Mn, TOC, SO42−, and NO3− were negatively correlated with depth, whereas As(V) and As(Total) did not show any correlation with depth, nor was As correlated with the amount and characteristics of DOM. High concentrations of As inhibited the metabolic activity of bacteria and thereby limited the production of fluorescent DOM. Sulfate-reducing bacteria transformed free-sulfate radicals to S2− and promoted the dissolution and fixation of arsenic. We identified three main forms of arsenic that varied with depth: FeOOH (absorption), COO (absorption), and FeAsS. Microbial communities also varied with depth, and Novosphingobium and Brevibacillus showed high relative abundances in the sediment profile. TOC and DOM were strongly depleted in strongly As-enriched depths.

Kinetics of arsenic and sulfur release from amorphous arsenic trisulfide

Arsenic trisulfide (As2S3) is known as one of the possible precipitates in arsenic removal from metallurgical waste streams. The advantage of precipitation in the form of arsenic trisulfide is its high arsenic content (up to 61% theoretically). However, arsenic trisulfide is unstable, especially under alkaline and oxidizing conditions, which is a significant barrier to arsenic fixation in the form of arsenic trisulfide. To further understand its stability, a series of laboratory leaching tests were performed under fully-controlled conditions to quantify the effect of pH, dissolved oxygen concentration, and temperature on the total arsenic and sulfur released. The experimental results show that the release rate of arsenic and sulfur increased with pH, the dissolved oxygen concentration, and temperature. In less alkaline conditions, the aqueous arsenic to sulfur ratio by weight was higher than the stoichiometric value of 1.6 in the solid As2S3, suggesting the formation of secondary phases or precipitates enriched in sulfur. The rate law derived from the kinetic modeling suggests that the rate-limiting step in the arsenic release process is the surface chemical reaction.