UV irradiation induced simultaneous reduction of Cu(II) and degradation of EDTA in Cu(II)-EDTA in wastewater containing Cu(II)-EDTA.

Decomplexation of Cu(II)-EDTA followed by chemical precipitation of free Cu(II) ions can effectively degrade EDTA in Cu(II)-EDTA and remove Cu(II), but requires large precipitant dosage and inevitably produces a large amount of copper-containing sludge that is difficult to deal with. Herein, we demonstrated that simultaneous reduction of Cu(II) and degradation of EDTA in Cu(II)-EDTA can be achieved by UV irradiation of wastewater containing Cu(II)-EDTA without adding reagent. 93.65% of Cu(II) was reduced to Cu(0) with a high purity of 99.93 wt%, which can be recycled, thus avoiding the generation of copper-containing sludge. 96.67% of EDTA in Cu(II)-EDTA was degraded, and the final products were HCHO, NH4+, NO3- and low-molecular acids. In depth, the dominant degradation mechanism of EDTA in Cu(II)-EDTA was photo-induced successive decarboxylation through homolysis of C-O and C-C bond of -CH2-COOH group, followed by ligand to metal charge transfer (LMCT) and hydrolysis reactions. The minor degradation mechanism of EDTA in Cu(II)-EDTA was successive decarboxylation by •OH radicals. Simultaneously, Cu(II) was reduced to Cu(0) by H• and eaq- produced by UV irradiation of Cu(II)-EDTA. This study provided an approach of simultaneous removal of heavy metals and degradation of EDTA in Cu(II)-EDTA in wastewater containing heavy metal-EDTA complex.

Mechanistic insights into Sb(III) and Fe(II) co-oxidation by oxygen and hydrogen peroxide: Dominant reactive oxygen species and roles of organic ligands.

Sole O2 or H2O2 oxidant hardly oxidize Sb(III) on a time scale of hours to days, but Sb(III) oxidation can simultaneously occur in Fe(II) oxidation by O2 and H2O2 due to the generation of reactive oxygen species (ROS). However, Sb(III) and Fe(II) co-oxidation mechanisms regarding the dominant ROS and effects of organic ligands require further elucidation. Herein, the co-oxidation of Sb(III) and Fe(II) by O2 and H2O2 was studied in detail. The results indicated that increasing the pH significantly increased Sb(III) and Fe(II) oxidation rates during Fe(II) oxygenation, while the highest Sb(III) oxidation rate and oxidation efficiency was obtained at pH 3 with H2O2 as the oxidant. HCO3- and H2PO4-anions exerted different effects on Sb(III) oxidation in Fe(II) oxidation processes by O2 and H2O2. In addition, Fe(II) complexed with organic ligands could improve Sb(III) oxidation rates by 1 to 4 orders of magnitude mainly due to more ROS production. Moreover, quenching experiments combined with the PMSO probe demonstrated that .OH was the main ROS at acidic pH, whereas Fe(IV) played a key role in Sb(III) oxidation at near-neutral pH. In particular, the steady-state concentration of Fe(IV) ([Fe(IV)]ss) and kFe(IV)/Sb(III) were determined to be 1.66×10-9 M and 2.57×105 M-1 s-1, respectively. Overall, these findings help to better understand the geochemical cycling and fate of Sb in Fe(II)- and DOM-rich subsurface environments undergoing redox fluctuations and are conductive to developing Fenton reactions for the in-situ remediation of Sb(III)-contaminated environments.

Effective reduction and recovery of As(III) and As(V) from alkaline wastewater by thiourea dioxide: Efficiency and mechanism.

For alkaline wastewater with high arsenic concentration, the traditional lime precipitation inevitably produces large amounts of hazardous waste. Herein, a heat-activated reduction method employing thiourea dioxide (TDO) as the reductant was proposed to efficiently remove and recover As(III)/As(V) from alkaline wastewater in the form of valuable As(0). More than 99.9% of As(III)/As(V) (2-400 mM) were reduced to As(0) with a high purity of more than 99.5 wt% by TDO within 30 min. The highly reductive eaq- and SO2- radical generated during TDO decomposition contribute to the arsenic reduction, and the contribution ratios of eaq- and SO2- radical were estimated to be approximately 57.6% and 42.4% for As(III) removal and 62.2% and 37.8% for As(V) removal, respectively. The arsenic reduction was greatly improved by increasing pH and temperature, which could accelerate the cleavage of C-S bond in TDO for the eaq- and SO2- formation. The presence of dissolved oxygen, which can not only scavenge eaq-/SO2- but also directly oxidize SO22-, had a negative effect on the arsenic removal. The presence of CO32- slightly suppressed the arsenic removal due to the eaq- scavenging effect while SiO32-, PO43-, Cl-, SO42- and NH4+ had negligible effects. The proposed method was a potential technology for the efficient removal and reduction of arsenic in alkaline wastewater.

Selective recovery of Cu(II) from strongly acidic wastewater by zinc dimethyldithiocarbamate: Affecting factors, efficiency and mechanism.

The selective recovery of copper from strongly acidic wastewater containing mixed metal ions remains a significant challenge. In this study, a novel reagent zinc dimethyldithiocarbamate (Zn(DMDC)2) was developed for the selective removal of Cu(II). The removal efficiency of Cu(II) reached 99.6% after 120 min reaction at 30°C when the mole ratio Zn(DMDC)2/Cu(II) was 1:1. The mechanism investigation indicates that the Cu(DMDC)2 products formed as a result of the displacement of Zn(II) from the added Zn(DMDC)2 by Cu(II) in wastewater, due to the formation of stronger coordination bonds between Cu(II) and the dithiocarbamate groups of Zn(DMDC)2. Subsequently, we put forward an innovative process of resource recovery for strongly acidic wastewater. Firstly, the selective removal of Cu(II) from actual wastewater using Zn(DMDC)2, with a removal efficiency of 99.7%. Secondly, high-value CuO was recovered by calcining the Cu(DMDC)2 at 800°C, with a copper recovery efficiency of 98.3%. Moreover, the residual As(III) and Cd(II) were removed by introducing H2S gas, and the purified acidic wastewater was used to dissolve ZnO for preparation of valuable ZnSO4·H2O. The total economic benefit of resource recovery is estimated to be 11.54 $/m3. Accordingly, this study provides a new route for the resource recovery of the treatment of copper-containing acidic wastewater.

Reductive removal of As(V) and As(III) from aqueous solution by the UV/sulfite process: Recovery of elemental arsenic.

The removal of arsenic (As(V) and As(III)) from contaminated water has attracted great attention. However, the generation of arsenic-containing hazardous waste by traditional methods has become an inevitable environmental problem. Herein, a UV/sulfite advanced reduction method was proposed to remove As(V) and As(III) from aqueous solution in the form of valuable elemental arsenic (As(0)), thus avoiding the generation of arsenic-containing hazardous waste. The results showed that greater than 99.9% of As(V) and As(III) were reduced to the high purity As(0) (> 99.5 wt%) with the residual arsenic concentration below 10 µg L-1. The hydrated electrons (eaq-), H• and SO3•- radicals are generated by the UV/sulfite process, of which eaq- and H• serve as reductants of As(V) and As(III) while the SO3•- radicals inhibit arsenic reduction by oxidizing arsenic. The effective quantum efficiency (Φ) for the formation of As(0) in the As(V) and As(III) removal process is approximately 0.0078 and 0.0055 mol/Einstein, respectively. The reduction of arsenic is favorable under alkaline conditions (pH > 9.0) due to the higher photolysis efficiency of SO32- than HSO3- (pKa = 7.2) and higher stability of eaq-/H• under alkaline conditions. The presence of dissolved oxygen (O2), NO2-, NO3-, CO32-, PO43- and humic acid (HA) inhibited arsenic reduction through light blocking or eaq-/H• scavenging effects while Cl-, SO42-, Ca2+ and Mg2+ had negligible effects on arsenic reduction. The proposed method can effectively remove and recover arsenic from contaminated water at a low cost, demonstrating feasibility for practical application. This study provides a novel technology for the reductive removal and recovery of arsenic from contaminated water.

H2S release rate strongly affects particle size and settling performance of metal sulfides in acidic wastewater: The role of homogeneous and heterogeneous nucleation.

Sulfide precipitation is an extensively used method to precipitate metal and arsenic from acidic wastewater, whereas the tiny and negatively-charged metal sulfides with poor settling performance are generated. The factors and mechanisms that influence particle size and settling performance remain unclear. Herein, the effects of sulfuration factors, e.g., reagent dosage, acidity and H2S release rate on the particle size and settling performance of metal sulfides were investigated, and involved mechanisms were systematically revealed. The results showed that the reagent dosage and acidity had a limited effect on particle size and settling performance while the H2S release rate played a critical role. Under homogeneous conditions, the decrease in H2S release rate, which can reduce the initial supersaturation and supply the sustainable supersaturation, increased the particle size of metal sulfides generated using Na2S solution. Under heterogeneous conditions, the decrease in H2S release rate further increased the particle size of metal sulfides generated using low-solubility CaS/FeS and further improved settling performance, in which heterogeneous nucleation played a crucial role besides supersaturation. The developed dissolution-diffusion-growth model qualitatively explained the negative relationship between H2S release rate and particle growth. This work provides implications for improving the settling performance of metal sulfides in acidic wastewater.

Reductive Removal and Recovery of As(V) and As(III) from Strongly Acidic Wastewater by a UV/Formic Acid Process.

The removal of arsenic (As(V) and As(III)) from strongly acidic wastewater using traditional neutralization or sulfuration precipitation methods produces a large amount of arsenic-containing hazardous wastes, which poses a potential threat to the environment. In this study, an ultraviolet/formic acid (UV/HCOOH) process was proposed to reductively remove and recover arsenic from strongly acidic wastewater in the form of valuable elemental arsenic (As(0)) products to avoid the generation of hazardous wastes. We found that more than 99% of As(V) and As(III) in wastewater was reduced to highly pure solid As(0) (>99.5 wt %) by HCOOH under UV irradiation. As(V) can be efficiently reduced to As(IV) (H2AsO3 or H4AsO4) by hydrogen radicals (H•) generated from the photolysis of HCOOH through dehydroxylation or hydrogenation. Then, As(IV) is reduced to As(III) by H• or through its disproportionation. The reduction of As(V) to H4AsO4 by H• and the disproportionation of H4AsO4 are the main reaction processes. Subsequently, As(III) is reduced to As(0) not only by H• through stepwise dehydroxylation but also through the disproportionation of intermediate arsenic species As(II) and As(I). With additional density functional theory calculations, this study provides a theoretical foundation for the reductive removal of arsenic from acidic wastewater.

Clean and effective removal of Cl(-I) from strongly acidic wastewater by PbO2.

Recycling strongly acidic wastewater as diluted H2SO4 after contaminants contained being removed was previously proposed, however, Cl(-I), a kind of contaminant contained in strongly acidic wastewater, is difficult to remove, which severely degrades the quality of recycled H2SO4. In this study, the removal of Cl(-I) using PbO2 was investigated and the involved mechanisms were explored. The removal efficiency of Cl(-I) reached 93.38% at 50℃ when PbO2/Cl(-I) mole ratio reached 2:1. The identification of reaction products shows that Cl(-I) was oxidized to Cl2, and PbO2 was reduced to PbSO4. Cl2 was absorbed by NaOH to form NaClO, which was used for the regeneration of PbO2 from the generated PbSO4. Cl(-I) was removed through two pathways, i.e., surface oxidation and •OH radical oxidation. •OH generated by the reaction of PbO2 and OH- plays an important role in Cl(-I) removal. The regenerated PbO2 had excellent performance to remove Cl(-I) after six-time regeneration. This study provided an in-depth understanding on the effective removal of Cl(-I) by the oxidation method.

A review on the removal of Cl(-I) with high concentration from industrial wastewater: Approaches and mechanisms.

Large quantities of wastewaters containing high concentrations of Cl(-I) can be generated in several industries when chloride-containing materials and additive agents are employed. Because Cl(-I) is unavailable to microorganisms, physicochemical methods are generally used for the removal of Cl(-I); however, as the most stable form of chlorine under aqueous conditions, Cl(-I) in wastewaters is difficult to remove to achieve low residual concentrations through common physicochemical methods. This paper provides new insights into traditional precipitation, oxidation, ion exchange and physical separation methods, as well as newly developed approaches, for Cl(-I) removal from various industrial wastewaters through analysis of the mechanisms, applicable conditions, optimum parameters, and method advantages and disadvantages. Moreover, the developmental trends and potential improvements to these approaches are also presented. Currently, precipitation is the most common and efficient Cl(-I) removal method, for which ultraviolet (UV) light is regarded as an effective means of improvement. Additionally, advanced oxidation processes (AOPs), where Cl(-I) can be oxidized to generate Cl radicals, Cl2- radicals, Cl2 gas, etc., show great promise for Cl(-I) removal. This review provides a theoretical foundation for the effective treatment and for the secondary utilization of industrial wastewaters containing Cl(-I).

Improving removal rate and efficiency of As(V) by sulfide from strongly acidic wastewater in a modified photochemical reactor.

Employing ultraviolet light to enhance the removal of As(V) by sulfide (S(-II)) from strongly acidic wastewater is a potential method. However, we found the arsenic trisulfide (As2S3) and elemental sulfur (S8) particles formed in this method not only vastly hinder light transmission in the wastewater but also undergo light-induced redissolution, leading to a decrease in removal rate and efficiency of As(V). Herein, As(V) removal by sulfide from strongly acidic wastewater was performed in a modified photochemical reactor to weaken the effect of the formed particles on As(V) removal. It was found that in this study, the formed particles could be efficiently removed from the photoreactor by three operations, i.e. circulation-filtration, septum setting, and lamp sleeve cleaning. The removal of As(V) was approximately 11-fold faster than that without three operations, saving 90.9% of the reaction time and 89.4% of energy consumption. The removal efficiency of As(V) also increased through weakening the light-induced redissolution of the formed particles. This study facilitates the practical application of the UV light promoted As(V) removal technology and also provides a new method to lessen the light-blocking effect in the particle-forming photochemical reaction systems.

Calcium sulfide-organosilicon complex for sustained release of H2S in strongly acidic wastewater: Synthesis, mechanism and efficiency.

Sulfide precipitation is an efficient method to remove Cu(II) and As(III) from strongly acidic wastewater, but the instantaneous release of H2S from traditional sulfuration reagents causes serious H2S pollution. Moreover, the obtained precipitates are mixtures of CuS and As2S3, leading to difficulties in resource recovery. In this study, a calcium sulfide-organosilicon complex (CaS-OSCS), in which CaS was coated into a matrix of {[O1.5Si(CH2)3NH]CS}n (OSCS) via the coordination bonding, was developed. OSCS, as a matrix of CaS-OSCS, can ensure the sustained and stable release of H2S under strongly acidic conditions owing to its low swelling (1.75% swelling ratio) and excellent acid resistance. The release longevity of H2S from CaS-OSCS extended from 5 min up to 50 min compared with that from CaS because the hydrophobic OSCS prevented solution diffusing to the pores of CaS-OSCS and thus slowed down the hydrolysis of CaS in pores. 99% of Cu(II)/As(III) was precipitated without H2S escape, and the dosage of sulfuration reagents was reduced by 30%. In addition, CaS-OSCS improved the selective separation of copper from wastewater, and a separation factor between Cu(II) and As(III) reached 2376. This study provides a potential approach for the elimination of H2S pollution and selective recovery of copper.

Recovery of Re(VII) from strongly acidic wastewater using sulphide: Acceleration by UV irradiation and the underlying mechanism.

Strongly acidic wastewater generated from the molybdenum and copper smelting process is of great value for recycling sulfuric acid and valuable metals, such as rhenium (Re). Herein, a high Re(VII) (HReO4) recovery efficiency of 99% within 35 min from strongly acidic wastewater was successfully achieved by using sulphide coupled with ultraviolet (UV) light, and soluble Re(VII) precipitated as Re2S7 in this process. Mechanistic experiments showed that the intermediate Re-S species (i.e., HReO3S) was the dominant limitation responsible for Re(VII) precipitation in the dark, and UV irradiation dramatically accelerated the generation and conversion of HReO3S by inducing the formation of HS• and H•. The H• produced from the photodissociation of H2S promoted HReO4 transformation to H2ReO4•, which rapidly reacted with HS• to produce HReO3S, accelerating the conversion of HReO4. The radical-induced acceleration can also take place during the HReO3S conversion by slowly introducing H2S into the strongly acidic wastewater to continuously produce H• and HS•. This work offers an insight into the improvement of Re(VII) recovery by UV light, which can be potentially applied into resource recovery from strongly acidic wastewater.

Chemical solidification/stabilization of arsenic sulfide and oxide mixed wastes using elemental sulfur: Efficiencies, mechanisms and long-term stabilization enhancement by dicyclopentadiene.

Large amounts of hazardous arsenic sulfide (As2S3) wastes are generated in many industries. These wastes, which are extremely unstable and can partially transform into highly soluble arsenic oxide (As2O3) and then transform into As2S3 and As2O3 mixed wastes (ASOW), are difficult to be solidified/stabilized using common binders. This study proposed a thermally initiated copolymerization method employing elemental sulfur (S8) to chemically solidify/stabilize ASOW. Under thermal conditions (140-200 °C), the elemental sulfur rings break and polymerize into diradical polymeric sulfur chains (•S-(S)m-S•). The ASOW is solidified/stabilized not only by transforming As2S3 into poly(As2S3-r-S) copolymers through copolymerization of •S-(S)m-S• with As2S3 but also by transforming As2O3 into As2S3 in the presence of poly(As2S3-r-S) copolymers. However, the sulfur chain in poly(As2S3-r-S) copolymers gradually crystallizes into S8 after long-term aging, resulting in the depolymerization of copolymers. Dicyclopentadiene (DCP) greatly improves the long-term stability of the solidified body through maintaining the sulfur chain form by forming highly stable poly(As2S3-r-S-r-DCP) copolymers. The solidified body showed high compressive strength (25.7 MPa) and low leaching concentration of arsenic (<1.2 mg L-1) even after 732 days of aging. This study provides a theoretical foundation for the S8-based chemical solidification/stabilization of ASOW as well as other sulfide-containing wastes.

Removal of Ni(II) from strongly acidic wastewater by chelating precipitation and recovery of NiO from the precipitates.

Strongly acidic wastewater produced in nonferrous metal smelting industries often contains high concentrations of Ni(II), which is a valuable metal. In this study, the precipitation of Ni(II) from strongly acidic wastewater using sodium dimethyldithiocarbamate (DDTC) as the precipitant was evaluated. The effects of various factors on precipitation were investigated, and the precipitation mechanism was also identified. Finally, the nickel in the precipitates was recovered following a pyrometallurgical method. The results show that, under optimised conditions (DDTC:Ni(II) molar ratio = 4:1; temperature = 25 °C), the Ni(II) removal efficiency reached 99.3% after 10 min. In strongly acidic wastewater, the dithiocarbamate group of DDTC can react with Ni(II) to form DDTCNi precipitates. Further recovery experiments revealed that high-purity NiO can be obtained by the calcination of DDTCNi precipitates, with the nickel recovery efficiency reaching 98.2%. The gas released during the calcination process was composed of NO2, CS2, H2O, CO2, and SO2. These results provide a basis for an effective Ni(II) recovery method from strongly acidic wastewater.

Photo-induced dissolution of Bi2O3 during photocatalysis reactions: Mechanisms and inhibition method.

Photo-induced dissolution greatly limits the application of Bi2O3 photocatalyst in water treatment. In this study, mechanisms for the photo-induced dissolution of Bi2O3 were proposed. (1) Under UV light, h+ forms and diffuses through Bi2O3. (2) The h+, which reaches the surface of Bi2O3 and can be regarded as a monatomic oxygen ion (OS-), is weakly bonded to the crystal lattice. (3) Two OS- combine and the generated (O-O)2- ionic group is oxidized by h+, resulting in the release of O2 and dissolution of Bi2O3. However, modification of Bi2O3 using polyaniline (PANI) greatly inhibits Bi2O3 dissolution under UV. Under the PANI to Bi2O3 mass ratio of 1.5%, the concentration of produced Bi3+ significantly decreased from 2.02 to 0.27 mg/m2 with a high methylene blue (MB) degradation efficiency of 98.3%, thanks to the separation of h+ from VB-Bi2O3 to HOMO-PANI. This study provided the theoretical foundation for the modification and application of Bi2O3 in water treatment.

A novel precipitant for the selective removal of fluoride ion from strongly acidic wastewater: Synthesis, efficiency, and mechanism.

The strongly acidic wastewater containing fluoride [F(-I)] is generally neutralized using lime, producing massive hazardous solid waste, which may present serious environmental risks. In this study, a novel precipitant, N,N'-Bis(3-(triethoxysilyl)propyl)thiourea, was developed for the selective removal of F(-I) from strongly acidic wastewater. The precipitant was synthesized using (3-aminopropyl)triethoxysilane and thiourea at a molar ratio of 2:1 under 160 â„ƒ. More than 90% of initial F(-I) was removed by the prepared precipitant from strong acidic wastewater produced by nonferrous metal smelting industry, and the residual F(-I) concentration decreased to below 100 mg/L. The F(-I) removal performance is almost free from the interference of coexisting ions. Only 6 kg/m3 of fluoride slag, which can be recycled as a concrete waterproofing agent, was produced. The F(-I) removal mechanism including substitution, polycondensation, ion exchange and complexation was clarified: ‒OH on Si atoms in the hydrolysis product of BTPT was substituted by F(-I), and a fluoro-substituted product formed; the polycondensation of BTPT and fluoro-substituted product produced polymer precipitates; the specific adsorption of F(-I) on the polymer precipitates occurred through ion exchange with ‒OH and complexation with -NH2+-.

Sulfate radical-based removal of chloride ion from strongly acidic wastewater: Kinetics and mechanism.

Specific to strongly acidic wastewater, the traditional lime neutralization produces massive hazardous waste and present serious environmental risks. Thus, the recycling of purified wastewater after the contained contaminants being removed has been proposed. However, among these contaminants, chloride ion (Cl(-I)) is rather difficult to remove. This study proposes a new method to remove Cl(-I) using thermal activated persulfate (PS). Under optimized conditions, above 96% of initial Cl(-I) was removed from the actual wastewater, and the residual Cl(-I) was below 158 mg/L, which satisfies the requirement of Cl(-I) concentration for wastewater recycling. Furthermore, the mechanism was investigated. In the strongly acidic wastewater, the high concentration of H+ prompted the thermal activation process of PS through two pathways. (1) H+ prompted the transformation of S2O82- into HSO4- and SO4, and then into HSO5- that was finally transformed into ·OH and ·SO4- at above 70 â„ƒ. (2) H+ prompted the production of ·OH through the transformation of ·SO4- into ·HSO4 and the cleavage of ·HSO4. The key step for Cl(-I) removal was identified as the formation of ·Cl or ·Cl2- from the oxidation of Cl(-I) by ·SO4- and ·OH, and their contribution ratios were estimated to be 67.4% and 32.6%, respectively.

Removal of Cl(-I) from strongly acidic wastewater containing Cu(II) by complexation-precipitation using thiourea: Efficiency enhancement by ascorbic acid.

Strongly acidic wastewater produced by copper smelting industries contains high concentrations of Cl(-I), Cu(II) and H2SO4. The common method for the treatment of this type of wastewater is neutralization, which produces large amounts of solid waste. To avoid the production of solid waste, it was proposed to selectively remove contaminants and then recycle the wastewater as diluted sulfuric acid. This study proposed a new complexation-precipitation method to effectively remove Cl(-I) using thiourea (TU) under the promotion of ascorbic acid (AC). The Cl(-I) removal efficiency was optimized, important effecting factors were investigated and the mechanisms of the AC-improved removal of Cl(-I) were studied. The results showed that, Cl(-I) removal efficiency reached 87.4 % under a TU/AC/Cl(-I) mole ratio of 1:3:1 and the residual Cl(-I) concentration was lowered from 1000 mg/L to 126.4 mg/L. The mechanism investigation showed that, AC first reduces Cu(II) to Cu(I), then, the produced Cu(I) is quickly complexed by TU to form the [Cu(I)x(TU)y]x+; finally, [Cu(I)x(TU)y]x+ precipitates with Cl(-I) in the form of [Cu(I)x(TU)y]Clx. This study provided a theoretical foundation of complexation-precipitation of Cl(-I) under strongly conditions and developed an effective method for removal of Cl(-I) from strongly acid waster.

Specific H2S Release from Thiosulfate Promoted by UV Irradiation for Removal of Arsenic and Heavy Metals from Strongly Acidic Wastewater.

The removal of arsenic and heavy metals (HMs) from strongly acidic wastewater by hydrogen sulfide (H2S) is an efficient method. However, traditional sulfuration reagents (Na2S, FeS, CaS, etc.) rapidly release H2S under acidic conditions via spontaneous hydrolysis, leading to serious H2S pollution. Herein, a H2S release process employing thiosulfate as a sulfuration reagent was proposed to eliminate H2S pollution. We found that thiosulfate can release H2S with specificity both in the dark and under ultraviolet (UV) irradiation under acidic conditions. In the absence of arsenic/HMs, H2S is not released because the formed H2S is consumed by a thiosulfate decomposition product, sulfite, or by its photolysis. In the presence of arsenic/HMs, H2S is released because the formed H2S immediately reacts with arsenic/HMs to generate sulfide precipitates rather than being consumed. The efficiency of transforming thiosulfate to H2S under UV irradiation is 2.5-fold the efficiency in the dark, because UV irradiation promotes the transformation of "effective sulfur" in thiosulfate molecules to form H2S through the transformation of HS· and S2O3• - radicals. Moreover, more than 99.9% of arsenic/HMs were removed from strongly acidic wastewater without producing H2S pollution under UV irradiation. This thiosulfate-based H2S-specific release process solves the problem of H2S pollution under acidic conditions.

UV-Improved Removal of Chloride Ions from Strongly Acidic Wastewater Using Bi2O3: Efficiency Enhancement and Mechanisms.

Strongly acidic wastewater generated from nonferrous metal smelting industries can be recycled as sulfuric acid after the contaminants have been removed, and among which, Cl- is rather difficult to remove. Although previous studies showed that Cl- can be removed from acidic Zn electrolyte by Bi2O3, this method still suffers from low efficiency when being employed for strongly acidic wastewater recycling. Otherwise, very high Bi2O3 dosage and H2SO4 concentration are required, leading to the need for improvement. In this study, UV irradiation was employed to improve the removal, and it was found that Cl- removal efficiency was substantially enhanced from 63.9 to 98.3%, the optimum Bi2O3/Cl- mole ratio was lowered from 1.5:1 to 0.5:1, and to achieve the maximum removal efficiency, the required H2SO4 concentration was lowered from 70 to 40 g/L. The mechanisms were also elaborated. First, Bi2O3 dissolves under the function of UV and H+, and the produced Bi3+ combines with H2O and Cl- to form BiOCl. Then, Bi2O3/BiOCl transforms into BiOCl(h+)/Bi2O3(e-) under UV irradiation, and the generated h+ oxidizes Cl- to Cl•. Finally, Cl• reacts with Bi2O3/e- to produce BiOCl. This study offered a theoretical foundation for the improvement of Cl- removal from strongly acidic wastewater.