Degradation of organic contaminants through the activation of oxygen using zero valent copper coupled with sodium tripolyphosphate under neutral conditions

In this study,sodium tripolyphosphate(STPP) was used to promote the removal of organic pollutants in a zero-valent copper(ZVC)/O_2 system under neutral conditions for the first time.20 mg/L p-nitrophenol(PNP) can be completely decomposed within 120 min in the ZVC/O_2/STPP system.The PNP degradation process followed pseudo-first-order kinetics and the degradation rate of PNP gradually increased upon the decreasing ZVC particle size.The optimal pH of the reaction system was 5.0.Our mechanism investigation showed that Cu~+generated by ZVC corrosion was the main reducing agent for the activation of 02 to produce ROS.-OH was identified as the only ROS formed during the degradation of PNP and its production pathway was the double-electron activation of O_2(O_2→H_2 O_2→·OH).In this process,STPP did not only promote the release of Cu~+through its complexation,but also promoted the production of OH by reducing the redox potential of Cu~(2+)/Cu~+.In addition,we could initiate and terminate the reaction by controlling the pH.At pH 8.1,ZVC/02/STPP could continuously degrade organic pollutants;at pH 8.1,the reaction was terminated.STPP was recycled to continuously promote the corrosion of ZVC and O_2 activation as long as the pH was 8.1.This study provided a new and efficient way for O_2 activation and organic contaminants removal.     

Combined zero valent iron and hydrogen peroxide conditioning significantly enhances the dewaterability of anaerobic digestate

The importance of enhancing sludge dewaterability is increasing due to the considerable impact of excess sludge volume on disposal costs and on overall sludge management. This study presents an innovative approach to enhance dewaterability of anaerobic digestate(AD) harvested from a wastewater treatment plant. The combination of zero valent iron(ZVI, 0–4.0 g/g total solids(TS)) and hydrogen peroxide(HP, 0–90 mg/g TS) under pH 3.0 significantly enhanced the AD dewaterability. The largest enhancement of AD dewaterability was achieved at 18 mg HP/g TS and 2.0 g ZVI/g TS, with the capillary suction time reduced by up to 90%. Economic analysis suggested that the proposed HP and ZVI treatment has more economic benefits in comparison with the classical Fenton reaction process. The destruction of extracellular polymeric substances and cells as well as the decrease of particle size were supposed to contribute to the enhanced AD dewaterability by HP + ZVI conditioning.     

Cysteine-enhanced reductive degradation of nitrobenzene using nano-sized zero-valent iron by accelerated electron transfer

As an aliphatic amino acid, cysteine (CYS) is diffuse in the living cells of plants and animals. However, little is known of its role in the reactivity of nano-sized zero-valent iron (NZVI) in the degradation of pollutants. This study shows that the introduction of CYS to the NZVI system can help improve the efficiency of reduction, with 30% more efficient degradation and a reaction rate constant nine times higher when nitrobenzene (NB) is used as probe compound. The rates of degradation of NB were positively correlated with the range of concentrations of CYS from 0 to 10 mmol/L. The introduction of CYS increased the maximum concentration of Fe(III) by 12 times and that of Fe(II) by four times in this system. A comparison of systems featuring only CYS or Fe(II) showed that the direct reduction of NB was not the main factor influencing its CYS-stimulated removal. The reduction in the concentration of CYS was accompanied by the generation of cystine (CY, the oxidized form of cysteine), and both eventually became stable. The introduction of CY also enhanced NB degradation due to NZVI, accompanied by the regeneration of CYS. This supports the claim that CYS can accelerate electron transfer from NZVI to NB, thus enhancing the efficiency of degradation of NB.     

Kinetics of antimony biogeochemical processes under pre-definite anaerobic and aerobic conditions in a paddy soil

While the transformation of antimony(Sb) in paddy soil has been previously investigated, the biogeochemical processes of highly chemical active Sb in the soil remain poorly understood. In addition, there is a lack of quantitative understanding of Sb transformation in soil. Therefore, in this study, the kinetics of exogenous Sb in paddy soils were investigated under anaerobic and aerobic incubation conditions. The dissolved Sb(V) and the Sb(V) extracted by diffusive gradient technique decreased u...     

A porous biochar supported nanoscale zero-valent iron material highly efficient for the simultaneous remediation of cadmium and lead contaminated soil

Risk associated with heavy metals in soil has been received widespread attention.In this study,a porous biochar supported nanoscale zero-valent iron（BC-nZVI） was applied to immobilize cadmium（Cd） and lead（Pb） in clayey soil.Experiment results indicated that the immobilization of Cd or Pb by BC-nZVI process was better than that of BC or nZVI process,and about 80% of heavy metals immobilization was obtained in BC-nZVI process.Addition of BC-nZVI could increase soil pH and organic matter（SOM）.Cd or...     

Phenol degradation in waters with high iodide level by layered double hydroxide-peroxodisulfate: Pathways and products

Recently, layered double hydroxide-peroxodisulfate (LDH-PDS) as an advanced oxidation system can effectively remove organics by the pathway of free radical. However, little has been known if there is a potential risk regarding the formation of high toxic iodine byproducts through another pathway when LDH-PDS is used in high iodide waters at coastal areas. Therefore, this study investigated phenol degradation pathways and transformation products to evaluate both removal mechanism and potential risk by LDH-PDS in high iodide waters. The results showed that in LDH-PDS system, with the degradation of PDS, phenol degraded till below detection limit in 1 hr in the presence of iodide, while PDS and phenol were hardly degraded in the absence of iodide, indicating iodide accelerated the transformation of PDS and the degradation of phenol. What is more, it reached the highest phenol removal efficiency under the condition of 100 mg/L LDH, 0.1 mmol/L PDS and 1.0 mmol/L iodide. In LDH-PDS system, iodide was rapidly oxidized by the highly active interlayer PDS, resulting in the formation of reactive iodine including hypoiodic acid, iodine and triiodide instead of free radicals, which contributed rapid degradation of phenol. However, unfortunately toxic iodophenols were detected. Specifically, 2-iodophenol and 4-iodophenol were formed firstly, afterwards 2,4-diiodophenol and 2,6-diiodophenol were produced, and finally iodophenols and diiodophenols gradually decreased and 2,4,6-Triiodophenol were produced. These results indicated that LDH-PDS should avoid to use in high iodide waters to prevent toxic iodine byproduct formation although iodide can accelerate phenol degradation.     

Coprecipitation mechanisms of Zn by birnessite formation and its mineralogy under neutral pH conditions

Birnessite (δ-Mn(IV)O₂) is a great manganese (Mn) adsorbent for dissolved divalent metals. In this study, we investigated the coprecipitation mechanism of δ-MnO₂ in the presence of Zn(II) and an oxidizing agent (sodium hypochlorite) under two neutral pH values (6.0 and 7.5). The mineralogical characteristics and Zn–Mn mixed products were compared with simple surface complexation by adsorption modeling and structural analysis. Batch coprecipitation experiments at different Zn/Mn molar ratios showed a Langmuir-type isotherm at pH 6.0, which was similar to the result of adsorption experiments at pH 6.0 and 7.5. X-ray diffraction and X-ray absorption fine structure analysis revealed triple-corner-sharing inner-sphere complexation on the vacant sites was the dominant Zn sorption mechanism on δ-MnO₂ under these experimental conditions. A coprecipitation experiment at pH 6.0 produced some hetaerolite (ZnMn(III)₂O₄) and manganite (γ-Mn(III)OOH), but only at low Zn/Mn molar ratios (< 1). These secondary precipitates disappeared because of crystal dissolution at higher Zn/Mn molar ratios because they were thermodynamically unstable. Woodruffite (ZnMn(IV)₃O₇•2H₂O) was produced in the coprecipitation experiment at pH 7.5 with a high Zn/Mn molar ratio of 5. This resulted in a Brunauer–Emmett–Teller (BET)-type sorption isotherm, in which formation was explained by transformation of the crystalline structure of δ-MnO₂ to a tunnel structure. Our experiments demonstrate that abiotic coprecipitation reactions can induce Zn–Mn compound formation on the δ-MnO₂ surface, and that the pH is an important controlling factor for the crystalline structures and thermodynamic stabilities.     

Liquid-phase hydrodechlorination of trichloroethylene driven by nascent H2 under an open system: Hydrogenation activity, solvent effect and sulfur poisoning

Hydrodechlorination is a promising technology for the remediation of water body contaminated with trichloroethylene (TCE). In this work, the liquid-phase hydrogenation of TCE by Raney Ni (R-Ni) and Pd/C under an open system have been studied, in which nascent H₂ (Nas-H₂) generated in situ from the cathode acted as a hydrogen source. Experimental results showed that TCE was completely eliminate from the solution through the synergistic effects of hydrodechlorination and air flotation due to the formation of continuous micro/nano-sized Nas-H₂ bubbles from the cathode. Furthermore, the effects of inorganic anions and organic solvents on R-Ni and Pd/C hydrogenation activity were investigated, respectively. The results showed that NO₃^? and acetonitrile can form a competitive reaction with TCE; Sulfur with lone-pair electrons will cause irreversible poisoning to these two catalysts, and have a stronger inhibitory effect on Pd/C. This work helps to realize the separation of volatile halogenated compounds from water environment and provides certain data support for the choice of catalyst in the actual liquid-phase hydrogenation system.     

A collaborative strategy for enhanced reduction of Cr(VI) by Fe(0) in the presence of oxalate under sunlight: Performance and mechanism

Nanometer-size zero-valent iron (NZVI) is an efficient reducing agent, but its surface is easily passivated with an oxide layer, leading to reaction inefficiency. In our study, oxalate (OA) was introduced into this heterogeneous system of NZVI, which could form ferrioxalate complexes with the NZVI surface-bound Fe³⁺ and dissolved Fe³⁺ in the solution. Photolysis of ferrioxalate complexes can facilitate the generation of Fe²⁺ from Fe³⁺ and CO₂^?- radical, both species have strong reduction capacity. Hence, a “photo-oxalate-Fe(0)” system through sunlight induction was established, which not only prohibited the formation of a surface passivation layer, but also displayed a synergetic mechanism of ferrioxalate photolysis to enhance reduction, exhibiting remarkably higher degradation activity (several times faster) toward the model pollutant Cr(VI) than the mechanism with NZVI alone. Factor tests suggested that both NZVI dosage and OA content markedly affected the reduction rate. Low pH was beneficial to the reduction efficiency. Moreover, recyclability experiment showed that the reduction rate decreased from 0.21706 to 0.03977 min^?1 after three cycles of reuse due to the NZVI losing reaction activity generally, but the system still maintained considerable reduction capacity. Finally, a mechanism was revealed whereby NZVI would transform to Fe oxides after the exhaustion of its reductive power, and the photolysis of ferrioxalate to promote the cycling of iron species played the predominant role in providing extra reduction ability. These features confirm that introduction of OA into Cr(VI) reduction by NZVI through sunlight induction is advantageous and promising.     

The impact of preozonation on the coagulation of cellular organic matter produced by Microcystis aeruginosa and its toxin degradation

Ozonation pretreatment is typically implemented to improve algal cell coagulation. However, knowledge on the effect of ozonation on the characteristics and coagulation of associated algal organic matter, particularly cellular organic matter (COM), which is extensively released during algal bloom decay, is limited. Hence, this study aimed to elucidate the impact of ozonation applied before the coagulation of dissolved COM from the cyanobacteria Microcystis aeruginosa. Additionally, the degradation of microcystins (MCs) naturally present in the COM matrix was investigated. A range of ozone doses (0.1–1.0 mg O₃/mg of dissolved organic carbon – DOC) and ozonation pH values (pH 5, 7 and 9) were tested, while aluminium and ferric sulphate coagulants were used for subsequent coagulation. Despite negligible COM removal, ozonation itself eliminated MCs, and a lower ozone dose was required when performing ozonation at acidic or neutral pH (0.4 mg O₃/mg DOC at pH 5 and 7 compared to 0.8 mg O₃/mg DOC at pH 9). Enhanced MC degradation and a similar pattern of pH dependence were observed after preozonation-coagulation, whereas coagulation alone did not sufficiently remove MCs. In contrast to the benefits of MC depletion, preozonation using ≥ 0.4 mg O₃/mg DOC decreased the coagulation efficiency (from 42%/48% to 28%–38%/41%–44% using Al/Fe-based coagulants), which was more severe with increasing ozone dosage. Coagulation was also influenced by the preozonation pH, where pH 9 caused the lowest reduction in COM removal. The results indicate that ozonation efficiently removes MCs, but its employment before COM coagulation is disputable due to the deterioration of coagulation.     

Efficient degradation of organic pollutants by S-NaTaO3/biochar under visible light and the photocatalytic performance of a permonosulfate-based dual-effect catalytic system

Removing large concentrations of organic pollutants from water efficiently and quickly under visible light is essential to developing photocatalytic technology and improving solar energy efficiency. This study used a simple hydrothermal method to prepare a non-metallic, S-doped NaTaO₃ (S-NTO) photocatalyst, which was then loaded onto biochar (BC) to form a S-NTO/BC composite photocatalyst. After uniform loading onto BC, the S-NTO particles transformed from cubic to spherical. The photogenerated electron-hole pair recombination probability of the composite photocatalyst was significantly lower than those of the NTO particles. The light absorption range of the catalyst was effectively widened from 310 nm UV region to visible region. In addition, a dual-effect catalytic system was constructed by introducing peroxymonosulfate (PMS) into the environment of the pollution to be degraded. The Rhodamine B, Methyl Orange, Acid Orange 7, tetracycline, and ciprofloxacin degradation efficiency at 40 mg/L reached 99.6%, 99.2%, 84.5%, 67.1%, and 70.7%, respectively, after irradiation by a 40 W lamps for 90 min. The high-efficiency visible-light catalytic activity of the dual-effect catalytic system was attributed to doping with non-metallic sulfur and loading of catalysts onto BC. The development of this dual-effect catalytic system provides new ideas for quickly and efficiently solving the problem of high-concentration organic pollution in aqueous environments, rationally and fully utilizing solar energy, and expanding the application of photocatalytic technology to practice.     

Enhanced activity of ZnS(111) by N/Cu co-doping:Accelerated degradation of organic pollutants under visible light

High-efficiency photocatalysts are of great significance for the application of photocatalytic technology in water treatment.In this study,N/Cu co-doped ZnS nanosphere photocatalys(N/Cu-ZnS) is synthesized by a hydrothermal method for the first time.After doping,the tex ture of nanosphere becomes loose,the nanometer diameter is reduced,making the specific surface area of catalyst increased from 34.73 to 101.59 m²/g.The characterization results show that more ZnS (111) crystal planes a...     

Peroxymonosulfate activation by Fe-N-S co-doped tremella-like carbocatalyst for degradation of bisphenol A: Synergistic effect of pyridine N, Fe-Nx, thiophene S

Bisphenol A (BPA) has received increasing attention due to its long-term industrial application and persistence in environmental pollution. Iron-based carbon catalyst activation of peroxymonosulfate (PMS) shows a good prospect for effective elimination of recalcitrant contaminants in water. Herein, considering the problem about the leaching of iron ions and the optimization of heteroatoms doping, the iron, nitrogen and sulfur co-doped tremella-like carbon catalyst (Fe-NS@C) was rationally designed using very little iron, S-C₃N₄ and low-cost chitosan (CS) via the impregnation-calcination method. The as-prepared Fe-NS@C exhibited excellent performance for complete removal of BPA (20 mg/L) by activating PMS with the high kinetic constant (1.492 min⁻¹) in 15 min. Besides, the Fe-NS@C/PMS system not only possessed wide pH adaptation and high resistance to environmental interference, but also maintained an excellent degradation efficiency on different pollutants. Impressively, increased S-C₃N₄ doping amount modulated the contents of different N species in Fe-NS@C, and the catalytic activity of Fe-NS@C-1-x was visibly enhanced with increasing S-C₃N₄ contents, verifying pyridine N and Fe-N_x as main active sites in the system. Meanwhile, thiophene sulfur (C-S-C) as active sites played an auxiliary role. Furthermore, quenching experiment, EPR analysis and electrochemical test proved that surface-bound radicals (^·OH and SO₄^⋅−) and non-radical pathways worked in the BPA degradation (the former played a dominant role). Finally, possible BPA degradation route were proposed. This work provided a promising way to synthesize the novel Fe, N and S co-doping carbon catalyst for degrading organic pollutants with low metal leaching and high catalytic ability.     

Anaerobic degradation of xenobiotic organic contaminants (XOCs): The role of electron flow and potential enhancing strategies

In groundwater, deep soil layer, sediment, the widespread of xenobiotic organic contaminants (XOCs) have been leading to the concern of human health and eco-environment safety, which calls for a better understanding on the fate and remediation of XOCs in anoxic matrices. In the absence of oxygen, bacteria utilize various oxidized substances, e.g. nitrate, sulphate, metallic (hydr)oxides, humic substance, as terminal electron acceptors (TEAs) to fuel anaerobic XOCs degradation. Although there have been increasing anaerobic biodegradation studies focusing on species identification, degrading pathways, community dynamics, systematic reviews on the underlying mechanism of anaerobic contaminants removal from the perspective of electron flow are limited. In this review, we provide the insight on anaerobic biodegradation from electrons aspect — electron production, transport, and consumption. The mechanism of the coupling between TEAs reduction and pollutants degradation is deconstructed in the level of community, pure culture, and cellular biochemistry. Hereby, relevant strategies to promote anaerobic biodegradation are proposed for guiding to an efficient XOCs bioremediation.