Arsenic Volatilization Research Articles

Green and efficient removal of arsenic and recovery of tin from hazardous waste tin refined copper slag

Arsenic contamination and low tin yields pose significant challenges in the utilization of copper slag for tin refining. Typically, tin in copper slag can be converted into a tin-rich concentrate or metallic tin via electrolysis, oxidation roasting, and acid leaching, facilitating tin resource recovery. However, copper slag roasting results in significant arsenic volatilization and environmental pollution. Herein, a novel copper slag treatment strategy for efficient tin recycling and arsenic removal. The thermodynamics of sulfuration reaction between copper slag and sulfur indicate that in the presence of sulfur, arsenic in copper slag can be converted into arsenic sulfide, effectively enhancing the arsenic thermostability. In addition, tin, cuprous sulfide, and iron are transformed into stable metal sulfides. The saturated vapor pressure of arsenic sulfide is higher than that of stannous sulfide, cuprous sulfide and iron sulfide. The conditions of sulfuration pretreatment were observed to be 1.6 times more sulfur, sulfuration temperature 573 K, and contact time of 4 h. The single vacuum distillation experiments for sulfides were carried out at 10 Pa and 1273 K held for 4 h to separate SnS, As2S3, and FeS, Cu2S. One-factor-at-a-time method was used to optimize operational parameters of secondary vacuum distillation, which include temperature and time. The optimum separation conditions of arsenic sulfide and stannous sulfide were 973 K and 2 h. The removal rate of arsenic is about 100%, and the purity of stannous sulfide is 99.9%. Arsenic is recovered as arsenic sulfide. This study will shed light on the development of new technologies for the treatment of arsenic-containing solid waste.

Mechanistic insights into the leaching and environmental safety of arsenic in ceramsite prepared from fly ash

Utilizing fly ash to prepare ceramsite is a promising way to immobilize heavy metals and recycle industrial solid waste. However, traditional preparation method of fly ash ceramsite has the disadvantages of large ignition loss. Therefore, the present study applied the pressure molding method to enhance solid content and improve the strength of ceramsite. The optimal preparation conditions of ceramsite were suggested as preheating at 450 °C for 25 min followed by sintering at 1050 °C for 30 min. Under such conditions, ceramsite with high compressive strength of 10.8 Mpa, bulk density of 878 kg m−3, and 1-h water absorption of 18.5% was fabricated, in compliance with Chinese standard (GB/T 1743.1–2010). The arsenic leaching concentration from the resulting product was considerably lower than Chinese standard (GB 5085.3–2007). Moreover, arsenic volatilization during ceramsite calcination was insignificant, and the vast majority of arsenic remained in resulting ceramsite. A geochemical speciation model developed for the multiple component system in ceramsite suggested that FeAsO4, Ca5(OH) (AsO4)3, and hydrous ferric oxide adsorption are the primary mechanisms retaining arsenic in ceramsite. Additionally, based on density functional theory calculations and biotoxicity test, the binding site of arsenic atom on mineral components and the environmental safety of ceramsite was determined and evaluated.

Experimental Study on the Recovery of Arsenic and Iron from Arsenic–Iron Precipitate by Carbon Thermal Magnetization Reduction

Arsenic–iron precipitate was treated using a carbon thermal magnetization reduction method in order to recover arsenic and iron. Arsenic–iron precipitate mixed with coke powder was roasted at a low temperature; arsenic was recovered in the form of As2O3, and iron was recovered in the form of Fe3O4. The volatilization rate of arsenic was 97.45%, and the content of arsenic in the precipitate was decreased to 0.60%. Iron and arsenic were recovered in the form of Fe3O4 and As2O3 with a purity of 99.91 wt.% under the conditions of a roasting temperature of 650 °C, coke powder addition of 25 wt.%, a roasting time of 180 min, and an argon flow rate of 10 L/min. The volatilization of arsenic was controlled by a chemical controlling step at 20–100 min, and this was switched to a diffusion controlling step at 120–180 min by kinetic experiments. The reaction mechanism of arsenic and iron under carbon thermal magnetization reduction was as follows: in the early stage of the reaction, a large amount of FeAsO4 was decomposed into As2O3 and Fe3O4; in the middle and late stages of the reaction, FeAsO4 was continuously decomposed and reduced, and the content of Fe3O4 was continuously increased until all iron was magnetized to generate Fe3O4, and the decomposed As2O3 volatilized into dust. Arsenic reacted with CaO to generate Ca3(AsO4)2, and this may be the reason why arsenic could not be removed completely.

Selective Separation of Arsenic from Arsenic-bearing Copper Dust by Vulcanization Reduction

Arsenic is removed from arsenic-bearing copper dust by vulcanizing reduction. Vulcanizing reduction conditions and kinetics of arsenic volatilization are studied. Different temperatures, sulfur additions and vulcanizing reduction times are studied to obtain the conditions of separating arsenic from arsenic-bearing copper dust. Arsenic was selectively removed with a volatilization rate of 94.54% under the conditions of temperature of 400°C, sulfur addition of 10wt% and 60min vulcanizing reduction time. Arsenic was prepared to As2O3 with a purity of 95.3% which can be used as raw material to prepare elemental arsenic. The kinetic study showed that the process of arsenic volatilization conformed to the SCM model; the arsenic volatilization process was controlled by diffusion control in the first 60 minutes and switched to chemical reaction in the 70-120 minutes.

Toxic Elements Behavior during Plasma Treatment for Waste Collected from Power Plants

The subject of this work is the treatment of solid waste collected from power plants using thermal plasma technology. Inductively coupled plasma (ICP), X-ray fluorescence (XRF), and energy-dispersive X-ray spectroscopy (EDX) were used to characterize the waste before and after the treatment. The results show that waste is formed essentially from carbon, but it also contains sulfur and toxic elements like lead, cadmium, zinc, and arsenic. For this reason, a plasma reactor was used to separate carbon from the heavy metals by a pyrolysis/combustion plasma system. After the plasma treatment, the mass of the waste was reduced by more than 85% and the metals were collected in the filter bag. A computer code was used to study the toxic element volatility during the treatment. With this code, the effects of plasma temperature, confinement matrix, and the composition of the carrier gas on the volatility of lead and arsenic were determined. The code results show that arsenic remains in the liquid phase for temperatures less than 2000 K, whereas for temperatures beyond 2100 K, arsenic becomes very volatile. For lead, any increase in temperature increases its vaporized quantity and its vaporization speed. The addition of oxygen in the carrier gas leads to the heavy metal incorporation in the confinement matrix. The increase of the quantity of Ba in the containment matrix strengthens the confinement of as in the matrix.

Mechanism of arsenic removal from tannin‐‑germanium complex augmented by ultrasound

The volatilization of arsenic (As) pollutes the environment; thus, it must be removed before preparing a germanium (Ge) concentrate. This study examined the As removal from tannin‑germanium complex (TGC) augmented by ultrasound and revealed the reaction scheme in the As removal process. Parameters such as ultrasound power, sulfuric acid (H2SO4) concentration, particle size, liquid solid ratio, and reaction temperature were studied systematically. Experimental results showed that the maximum As removal efficiency augmented by ultrasound was 92.0% under the optimum purifying parameters of ultrasound power of 225 W, H2SO4 concentration of 20 g/L, particle sizes of 74–96 μm, liquid solid ratio of 7/1 mL/g, reaction temperature of 40 °C, and reaction time of 30 min. This removal efficiency is 11.2% higher than those of conventional methods under the same reaction conditions. The loss rate of Ge was only 4.9% under the optimal reaction conditions. Mechanism analysis showed that ultrasound can destroy the packaging structure of the raw materials and enhance the porosity, thus strengthen the reaction kinetics.

An efficient and clean method for the selective separation of arsenic from scrap copper anode slime containing high arsenic and tin

As the different properties of conventional copper anode slime and scrap copper anode slime (SCAS), the disposal of arsenic before the extraction process is very important. There was simultaneous leaching of As and Sn when the hydrometallurgical process or the sulfation roasting-leaching was applied to treat arsenic in the SCAS. It was difficult to achieve the effective separation of arsenic and tin by these methods. Therefore, an effective and clean pretreatment method for selectively separating arsenic from scrap copper anode slime containing high arsenic and tin via oxygen-enriched roasting followed by acid leaching was proposed. The volatilization rate of arsenic was only 1.13% under the optimum oxygen-enriched roasting parameters. The results of acid leaching showed that the leaching efficiencies of Cu and As were above 97%, and the elements of Sn, Pb, and Ag were enriched in the leaching residue. It is a promising method which can not only obtain selective leachable compounds (such as insoluble SnO2) but also restrict the volatilization of arsenic by forming (MeO)x(As2O5)y or As2O5 to solve the problem of easy dispersion of arsenic, both of which were good for sulfuric acid leaching. Meanwhile, there was no need to develop a new process for treating the leachate, which can be directly sent to the electrolyte purification process.

Volatilization characteristics and relationship of arsenic and sulfur during coal pyrolysis

Similarities concerning the occurrence of arsenic and sulfur in coal are the reasons for studying the relationship between the volatilization of arsenic and sulfur during the pyrolysis process. For this purpose, three coals with different arsenic and sulfur contents were selected. Combined application of electron probe microanalysis (EPMA) and sequential chemical extraction determined the relationship between the speciation of arsenic and sulfur (especially pyrite) in coal. Effects of temperature and speciation on the volatilization of arsenic and sulfur were discussed. Results show that arsenic in all coals is significantly enriched in the distribution area of pyrite. The volatilization ratio of sulfur and arsenic increases with temperature, and their volatilization mainly occurs at 300–600 °C. Before 500 °C, aliphatic sulfur and organic arsenous are the main contributors to the volatilization of sulfur and arsenic, respectively. At 500–600 °C, the volatile sulfur and arsenic mainly come from the decomposition of pyrite. A characteristic peak is observed for the volatilization rate of arsenic and sulfur, and it almost coincided with the weight loss peak of coal. Moreover, the simultaneous volatilization behavior of arsenic and sulfur is observed in Gansu (GS) coal at 400 °C due to the devolatilization of coal and in Chongqing (CQ) coal at 550 °C due to the decomposition of pyrite. Sulfate in coal has a negative effect on the volatilization of arsenic. The possible reaction paths were predicted by the thermodynamic analysis of FactSage 7.3 software. Fe2O3 and CaS could adsorb arsenic to form stable arsenate (FeAsO4 and Ca3(AsO4)2) during the pyrolysis process.

Inhibition of methanogenesis leads to accumulation of methylated arsenic species and enhances arsenic volatilization from rice paddy soil

Flooded soils are important environments for the biomethylation and subsequent volatilization of arsenic (As), a contaminant of global concern. Conversion of inorganic to methylated oxyarsenic species is thought to be the rate-limiting step in the production and emission of volatile (methyl)arsines. While methanogens and sulfate-reducing bacteria (SRB) have been identified as important regulators of methylated oxyarsenic concentrations in anaerobic soils, the effects of these microbial groups on biovolatilization remain unclear. Here, microcosm and batch incubation experiments with an Arkansas, USA, rice paddy soil were performed in conjunction with metabolic inhibition to test the effects of methanogenic activity on As speciation and biovolatilization. Inhibition of methanogenesis with 2-bromoethanesulfonate (BES) led to the accumulation of methylated oxyarsenic species, primarily dimethylarsinic acid (DMAs(V)), and a four-fold increase in As biovolatilization compared to a control soil. Our results support a conceptual model that methanogenic activity suppresses biovolatilization by enhancing As demethylation rates. This work refines understanding of biogeochemical processes regulating As biovolatilization in anaerobic soil environments, and extends recent insights into links between methanogenesis and As metabolism to soils from the mid-South United States rice production region.

Separation of arsenic and tin from Cu–As alloy based on phase transformation in a vacuum to form Cu–Fe–S compounds

Cu–As alloy is viewed as one kind of secondary copper resources. It is difficult to simultaneously recover copper and remove arsenic using conventional processes. To separate arsenic and tin from Cu–As alloy (mainly Cu3As), an innovative methodology that uses vacuum distillation in the presence of pyrite to form new phase is proposed herein. The constituents, phases and morphology of the sample before and after vacuum distillation were investigated by chemical analysis, X-ray diffraction (XRD) analysis and electron probe microanalysis (EPMA) to interpret separation performances and volatilization mechanisms of arsenic and tin. Chemical analysis results showed that it is difficult to separate arsenic from Cu-As alloy by direct vacuum distillation, but arsenic and tin were effectively separated after introducing pyrite. The effects of several factors, such as temperature, pyrite dosage and distillation time, on separation performances of arsenic and tin were examined. Volatilization ratios of copper, arsenic and tin reached 0.84%, 96.29% and 88.70%, respectively. Results of XRD analysis and EPMA revealed that arsenic had strong affinity to copper in Cu-As alloy, which inhibited free volatilization of arsenic. After introduction of pyrite, formation of copper sulfides, such as mainly Cu5.433Fe1.087S4, Cu1.96S and Cu9S5, destroyed the alloy structure, which made elemental arsenic volatilize. Excessive sulfur also interacted with elemental arsenic to form mainly As4S3 that is also easily volatilized. Nevertheless, tin was only separated in the form of SnS. It is a promising method to achieve cleaner utilization of Cu-As alloy and effective control of arsenic pollution.

Biotransformation and removal of arsenic oxyanions by Alishewanella agri PMS5 in biofilm and planktonic states

Arsenic oxyanions are toxic chemicals that impose a high risk to humans and other living organisms in the environment. The present study investigated indigenous heterotrophic bacteria in the tailings dam effluent (TDE) of a gold mining factory. Thirty-seven arsenic resistant bacteria were cultured on Reasoner's 2A agar supplemented with arsenic salts through filtration. One strain encoded as PMS5 with the highest resistance to 140-mM sodium arsenite and 600-mM sodium arsenate in tryptic soy broth was selected for further investigations. According to phenotypic examinations and 16S rDNA sequence analysis, PMS5 belonged to the genus Alishewanella and was sensitive to most of the examined antibiotics. The biosorption and bioaccumulation abilities of arsenic salts were observed in this isolate based on Scanning Electron Microscopy (SEM) with Energy Dispersive X-Ray Analysis (EDX) and biosorption and bioaccumulation data. PMS5 was also found to cause the volatilization and biotransformation of arsenic oxyanions through their oxidation and reduction. Moreover, the contribution of PMS5 to arsenic (3+, 5+) bioprocessing under oligotrophic conditions was confirmed in fixed-bed reactors fed with the TDE of the gold factory (R1) and synthetic water containing As5+ (R2). According to biofilm assays such as biofilm staining, cell count, detachment assay and SEM, the arsenic significantly reduced the biofilm density of the examined reactors compared to that of the control (R3). Arsenate reduction and arsenite oxidation under bioreactor conditions were respectively obtained as 75.5–94.7% and 8%. Furthermore, negligible arsenic volatilization (1.2 ppb) was detected.

Effect of Fe-Mn-La-modified biochar composites on arsenic volatilization in flooded paddy soil.

As can be volatilized naturally; however, this has adverse environmental effects. In this study, we investigated As volatilization in flooded paddy soil with the addition of biochar (BC) and Fe-Mn-La-modified BC composites (FMLBCs). The addition of BC and FMLBCs caused decreases in total As volatilization in the soil over 7 weeks. Maximum volatilization was achieved in the third week followed by stabilization. Volatilization decreased by 21.9%, 18.8%, 20.8%, and 31.1% with the addition of BC, FMLBC1, FMLBC2, and FMLBC3 (BC/Fe/Mn/La weight ratios different), respectively, in lightly contaminated soil, and by 15.2%, 20.5%, 17.6%, and 25.4%, respectively, in highly contaminated soil. The FMLBCs decreased the exchangeable As fractions and increased the non-swappable As in the soil. Furthermore, the addition of FMLBCs significantly reduced the As(III) concentration in a suspended solution (P < 0.05), whereas no significant changes were observed in the As(V) or methyl arsenic acid concentrations. Soil enzyme activity increased and the relative abundances of Proteobacteria and Actinobacteria changed with the addition of FMLBCs. Therefore, the mechanism by which FMLBCs affected As volatilization likely included the following two aspects: (1) FMLBCs affected the transformation and distribution of soil As and decreased As dissolution, crystallization, and methylation; (2) FMLBCs influenced soil properties, which directly affected microorganism activity, thereby affecting As volatilization. FMLBCs therefore can decrease As volatilization properties and be used to control As volatilization in As-contaminated paddy soils.

Effect of atmospheric H2O2 on arsenic methylation and volatilization from rice plants and paddy soil

Studies focusing on arsenic methylation and volatilization in paddy soil, aiming to limit bioaccumulation of arsenic (As) in rice grains, have attracted global attention. In this study, we explored three aspects of these topics. First, rainwater and trace H2O2 were compared for their influence on the arsenic methylation and volatilization of paddy soil in different rice growth stages. Second, the arsenic accumulation in different parts of rice was affected by rainwater and trace H2O2. Third, we determined whether rice fields were affected by rainwater and trace H2O2. The result showed that the rainwater or trace H2O2 irrigation caused As(III) to significantly decrease and As(V) to significantly increase in soil. A similar consequence occurred in the filling stage and mature stage of rice. The arsenic volatilization rates of the rainwater and trace H2O2 irrigation were significantly higher than the control, and the arsenic volatilization of rainwater irrigation was the highest (51.0 μg m−2 d−1) in the filling stage. Compared to the control, the total arsenic and iAs of treatments decreased by 14–41% and 12–32% respectively. Finally, we found that rainwater and trace H2O2 irrigation likely increased rice fields.

Arsenic removal from copper slag matrix by high temperature sulfide-reduction-volatilization

Arsenic contamination has been a major problem in copper slag utilization. Arsenic is easily incorporated into the silicate-based matrix, making the arsenic difficult to volatilize. In this study, pyrite was selected to depolymerize the matrix structure and volatilize the glassy arsenic by sulfide-reduction-volatilization reaction. The optimum technological parameters and mechanism of glassy arsenic volatilization by pyrite were further studied. The optimum operating parameters for glassy arsenic volatilization by pyrite were determined to be a temperature of 1200 °C, a holding time of 60 min, a heating rate of 5 °C/min, a basicity of 0.3, and a pyrite addition content of 15%. The arsenic volatilization ratio reached 80.9% under these experimental conditions. Besides, the mechanism of glassy arsenic volatilization was elucidated by XRD, XPS, FTIR, and SEM analyses. These results indicate that, with the increase in temperature, the pyrite decomposes to generate a variety of sulfur-based reducing substances (FeS, FeS1-x, S2(g)). Through “oxygen capture reaction”, these sulfur-based reducing substances depolymerize the bridging oxygen structure from the glass former ([AsO4], [FeO4], and [SiO4]) by the conversion of (Q2 +Q3)→(Q0 +Q1) and result in the precipitation of glass former ([AsO4], [FeO4] and [SiO4]) combining with the nearby cation. In this process, the glassy arsenic is released by the glass network and participates in reductive volatilization reaction with sulfur-based reducing substances, converting the glassy arsenic with high thermal stability to volatile arsenic oxide and arsenic sulfide. These findings provide a theoretical support for the in situ volatilization of arsenic in copper smelting and centralized control of arsenic contamination.

Increase in arsenic methylation and volatilization during manure composting with biochar amendment in an aeration bioreactor

Biochar is widely used as an amendment to optimize the composting process. In this study, we firstly investigated the effects of biochar amendment on methylation and volatilization of arsenic (As), and the microbial communities during manure composting. Biochar amendment was found to increase the concentrations of monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) during mesophilic (days 0–10) and early thermophilic (days 11–15) phases, and promote As volatilization during the maturing phase (days 60–80) of composting. In addition, the abundances of As(V) reductase (arsC) and As(III) S-adenosyl-L-methionine methyltransferase (arsM) genes were higher in the biochar treatment than that in the control. Moreover, biochar amendment influenced the microbial communities by promoting As methylation and volatilization via Ensifer and Sphingobium carrying arsC genes, and Rhodopseudomonas and Pseudomonas carrying arsM genes. This study emphasized the considerable role of biochar on methylation and volatilization of As during manure composting and provided an overall characterization of the community compositions of arsC and arsM genes during manure composting. It will broaden our insights in As biogeochemical cycle during manure composting with biochar amendment, which will facilitate the regulation of As during manure composting and its application in agricultural soil.

A Model for Predicting Arsenic Volatilization during Coal Combustion Based on the Ash Fusion Temperature and Coal Characteristic

Arsenic emission from coal combustion power plants has attracted increasing attention due to its high toxicity. In this study, it was found that there was a close relationship between the ash fusion temperature (AFT) and arsenic distribution based on the thermodynamic equilibrium calculation. In addition to the AFT, coal characteristics and combustion temperature also considerably affected the distribution and morphology of arsenic during coal combustion. Thus, an arsenic volatilization model based on the AFT, coal type, and combustion temperature during coal combustion was developed. To test the accuracy of the model, blending coal combustion experiments were carried out. The experimental results and published data proved that the developed arsenic volatilization model can accurately predict arsenic emission during co-combustion, and the errors of the predicted value for bituminous and lignite were 2.3–9.8%, with the exception of JingLong (JL) coal when combusted at 1500 °C.

Pyrometallurgical Removal of Arsenic from Electrostatic Precipitators Dusts of Copper Smelting

This work describes the experimental results of pyrometallurgical removing of arsenic from the dust collected in the electrostatic copper precipitators within the gas cleaning system of a Copper Flash Smelting Furnace. The generation of dust in the copper smelting worldwide ranges from 2 - 15 wt% per ton of a copper concentrate. In Chile, copper smelters produce approximately 110 kt/y of dust with a concentration of arsenic between 1 and 15 wt%. The dust is a complex of metals oxides and sulfurs with copper concentrations greater than 10 wt% and relatively high silver concentrations. Since its high arsenic concentration, it is difficult to recover valuable metals through hydrometallurgical processes or by direct recirculation of the dust in a smelting furnace. Thus, the development of pyrometallurgical processes aimed at reducing the concentration of arsenic in the dust (<0.5 wt%) is the main objective of this study, giving particular attention to the production of a suitable material to be recirculated in operations of copper smelting. The work provides a detailed characterization of the dust including the Quantitative Evaluation of Minerals by Scanning Electron Microscopy (QEMSCAN), Scanning Electron Microscope-Energy Dispersive X-ray Analysis (SEM/EDS), X-Ray Diffraction (XRD), the elemental chemical analysis using Atomic Adsorption (AAS), and X-Ray Fluorescence (X-RF). By considering that arsenic volatilization requires a process of sulfidation-decomposition-oxidation, this work seeks to explore the roasting of mixtures of copper concentrate/dust, sulfur/dust, and pyrrhotite/dust. By the elemental chemical analysis of the mixture after and before the roasting process, the degree of arsenic volatilization was determined. The results indicated the effects of parameters such as roasting temperature, gas flow, gas composition, and the ratio of mixtures (concentrate/dust, sulfur/dust, or pyrrhotite/dust) on the volatilization of arsenic. According to the findings, the concentration of arsenic in the roasted Flash Smelting dust can be reduced to a relatively low level (<0.5 wt%), which allows its recirculation into an smelting process.

Characterization and Pyrometallurgical Removal of Arsenic from Copper Concentrate Roasting Dust

This paper describes the experimental results of removing arsenic from the dust collected in electrostatic precipitators of a fluidized bed roasting furnace (RP dust). The fluidized bed roasting process generates 600 kilotons of copper concentrate per year with 3 - 6 wt% of concentration of arsenic, producing a roasted product with a low content of arsenic below 0.3 wt%. The process generates 27 kilotons of RP dust per year with a concentration of arsenic of the order of 5 wt% and copper concentration of around 20 wt%. Subsequently, the dust collected in the electrostatic precipitators is treated by hydrometallurgical methods allowing the recovery of copper, and the disposition of arsenic as scorodite. This work proposes to use a pyrometallurgy process to the volatilization of arsenic from RP dust. The obtained material can be recirculated in copper smelting furnaces allowing the recovery of valuable metals. The set of experiments carried out in the roasting of the mixture of copper concentrate/RP dust and sulfur/RP dust used different ratios of mixtures, temperatures and roasting times. By different techniques, the characterization of the RP dust determined its size distribution, morphology, and chemical and mineralogical composition. RP dust is a composite material of small particles (<5 μm) in 50 μm agglomerates, mostly amorphous, with a complex chemical composition of sulfoxides. The results of the roasting experiments indicated that for a 75/25 weight ratio of the mixture of the copper concentrate/PR dust under 700℃, 15 minutes of roasting time with injection of air, the volatilization of arsenic reached 96% by weight. The arsenic concentration after the roasting process is less than 0.3% by weight. For a 5/95 mixture of sulfur/RP dust, at 650℃, the volatilization of arsenic reached a promissory result of 67%. Even that this study was carried out for a particular operation, the results have the potential to be extended to dust produced in the roasting of concentrates of nickel, lead-zinc, and gold.

Anaerobic biotransformation of roxarsone regulated by sulfate: Degradation, arsenic accumulation and volatilization

Roxarsone, an extensively used organoarsenical feed additive, is often pooled in livestock wastewater. Sulfate exists ubiquitously in livestock wastewater and is capable for arsenic remediation. However, little is known about impacts of sulfate on roxarsone biotransformation during anaerobic digestion of livestock wastewater. In this study, the biodegradation of 5.0 mg L−1 roxarsone, and the accumulation and volatilization of the generated arsenical metabolites in a sulfate-spiked upflow anaerobic granular blanket reactor were investigated. Based on the analysis of degradation products, the nitro and arsenate groups of roxarsone were successively reduced to amino and arsenite groups before the C–As bond cleavage. Effluent arsenic concentration was ∼0.75 mg L−1, of which 82.9–98.5% were organoarsenicals. The maximum arsenic volatilization rate reached 32.6 μg-As kg−1-VS d−1. Adding 5.0 mg L−1 sulfate enabled 66.7% and 45.9% decrease in inorganic arsenic concentration and arsenic volatilization rate, respectively. Arsenic content in the anaerobic granular sludge (AGS) was accumulated to 1250 mg kg−1 within 420 days. Based on the results of FESEM-EDS and XPS, sulfate addition induced arsenic precipitation in the AGS through the formation of orpiment. Arsenic in the effluent, biogas and AGS accounted for 52.9%, 0.01% and 47.1% of the influent arsenic when the reactor operated stably. The findings from this study suggest that sulfate has effectively regulatory effects on arsenic immobilization and volatilization during anaerobic digestion of organoarsenic-contaminated livestock wastewater.

The mechanism of polystyrene microplastics to affect arsenic volatilization in arsenic-contaminated paddy soils

Different concentrations and sizes of polystyrene microplastics (PS-MP) were added to low (25.9) and high (56.8) mg kg−1 As-contaminated soil to investigate the effects of PS-MP on soil As volatilization. Either S1 (10 μm) or S2 (0.1–1 μm) PS-MP was added to As-contaminated soil at 0.8%, which increased As volatilization by 13.7% and 7.4% in low As-contaminated soil; and 21.8% and 16.5% in high As-contaminated soil, respectively. The addition of PS-MP reduced the water-soluble (WS) As content, increased the non-specifically-sorbed (NSS), specifically-sorbed (SS) As content, soil catalase (CAT) and urease (UE) activities. The abundance of Proteobacteria and Firmicutes showed opposite trends to As volatilization, while the abundance of Bacteroidetes and arsM gene expression exhibited similar variability to As volatilization over the 7-week experiment. Therefore, we postulate that in As-contaminated soil, As volatilization was enhanced in the presence of PS-MP due to two possible mechanisms: 1) PS-MP affects the abundance of Proteobacteria, Firmicutes, Bacteroidetes, and arsM gene in soil; 2) PS-MP increases As volatilization via reducing soil nutrient and increasing the content of SS As. Our results highlighted the importance of investigating impacts of microplastics on the volatility of specific contaminants to implement effective environmental remediation strategies in polluted farmlands.