Enhanced carbon tetrachloride degradation by hydroxylamine in ferrous ion activated calcium peroxide in the presence of formic acid

• Complete CT degradation was achieved by employing HA to CP/Fe(II)/FA process. • Quantitative detection of Fe(II) regeneration and HO• production was investigated. • Benzoic acid outcompeted FA for the reaction with HO•. • CO₂•⁻ was the dominant reductive radical for CT removal. • Effects of solution matrix on CT removal were conducted. Hydroxyl radicals (HO•) show low reactivity with perchlorinated hydrocarbons, such as carbon tetrachloride (CT), in conventional Fenton reactions, therefore, the generation of reductive radicals has attracted increasing attention. This study investigated the enhancement of CT degradation by the synergistic effects of hydroxylamine (HA) and formic acid (FA) (initial [CT] = 0.13 mmol/L) in a Fe(II) activated calcium peroxide (CP) Fenton process. CT degradation increased from 56.6% to 99.9% with the addition of 0.78 mmol/L HA to the CP/Fe(II)/FA/CT process in a molar ratio of 12/6/12/1. The results also showed that the presence of HA enhanced the regeneration of Fe(II) from Fe(III), and the production of HO• increased one-fold when employing benzoic acid as the HO• probe. Additionally, FA slightly improves the production of HO•. A study of the mechanism confirmed that the carbon dioxide radical (CO₂•⁻), a strong reductant generated by the reaction between FA and HO•, was the dominant radical responsible for CT degradation. Almost complete CT dechlorination was achieved in the process. The presence of humic acid and chloride ion slightly decreased CT removal, while high doses of bicarbonate and high pH inhibited CT degradation. This study helps us to better understand the synergistic roles of FA and HA for HO• and CO₂•⁻ generation and the removal of perchlorinated hydrocarbons in modified Fenton systems.     

Toward better understanding vacuum ultraviolet–iodide induced photolysis via hydrogen peroxide formation,iodine species change,and difluoroacetic acid degradation

• UV/VUV/I^– induces substantial H₂O₂ and IO₃^– formation, but UV/I^– does not. • Increasing DO level in water enhances H₂O₂ and iodate productions. • Increasing pH decreases H₂O₂ and iodate formation and also photo-oxidation. • The redox potentials of UV/VUV/I^– and UV/VUV changes with pH changes. • The treatability of the UV/VUV/I^– process was stronger than UV/VUV at pH 11.0. Recently, a photochemical process induced by ultraviolet (UV), vacuum UV (VUV), and iodide (I^–) has gained attention for its robust potential for contaminant degradation. However, the mechanisms behind this process remain unclear because both oxidizing and reducing reactants are likely generated. To better understand this process, this study examined the evolutions of hydrogen peroxide (H₂O₂) and iodine species (i.e., iodide, iodate, and triiodide) during the UV/VUV/I^– process under varying pH and dissolved oxygen (DO) conditions. Results show that increasing DO in water enhanced H₂O₂ and iodate production, suggesting that high DO favors the formation of oxidizing species. In contrast, increasing pH (from 6.0 to 11.0) resulted in lower H₂O₂ and iodate formation, indicating that there was a decrease of oxidative capacity for the UV/VUV/I^– process. In addition, difluoroacetic acid (DFAA) was used as an exemplar contaminant to verify above observations. Although its degradation kinetics did not follow a constant trend as pH increases, the relative importance of mineralization appeared declining, suggesting that there was a redox transition from an oxidizing environment to a reducing environment as pH rises. The treatability of the UV/VUV/I^– process was stronger than UV/VUV under pH of 11.0, while UV/VUV process presented a better performance at pH lower than 11.0.     

PM-support interfacial effect and oxygen mobility in Pt,Pd or Rh-loaded (Ce,Zr,La)O2 catalysts

• Pt/CZL exhibits the optimum catalytic performance for HC and NO_x elimination. • The strong PM-Ce interaction favors the oxygen mobility and DOSC. • Pd/CZL shows higher catalytic activity for CO conversion due to more O_latt species. • Great oxygen mobility at high temperature broadens the dynamic operation window. • The relationship between DOSC and catalytic performance is revealed. The physicochemical properties of Pt-, Pd- and Rh- loaded (Ce,Zr,La)O₂ (shorted for CZL) catalysts before/after aging treatment were systematically characterized by various techniques to illustrate the relationship of the dynamic oxygen storage/release capacity and redox ability with their catalytic performances for HC, NO_x and CO conversions. Pt/CZL catalyst exhibits the optimum catalytic performance for HC and NO_x elimination, which mainly contribute to its excellent redox ability and dynamic oxygen storage/release capacity (DOSC) at lower temperature due to the stronger PM (precious metals)-support interaction. However, the worse stability of Pt-O-Ce species and volatile Pt oxides easily result in the dramatical decline in catalytic activity after aging. Pd/CZL shows higher catalytic activity for CO conversion by reason of more O_latt species as the active oxygen for CO oxidation reaction. Rh/CZL catalyst displays the widest dynamic operation window for NO_x elimination as a result of greater oxygen mobility at high temperature, and the ability to retain more Rh-O-Ce species after calcined at 1100°C effectively restrains sintering of active RhO_x species, improving the thermal stability of Rh/CZL catalyst.     

The performance of nitrate-reducing Fe(II) oxidation processes under variable initial Fe/N ratios: The fate of nitrogen and iron species

•Bacterially-mediated coupled N and Fe processes examined in incubation experiments. •NO₃⁻ reduction was considerably inhibited as initial Fe/N ratio increased. •The maximum production of N₂ occurred at an initial Fe/N molar ratio of 6. •Fe minerals produced at Fe/N ratios of 1–2 were mainly easily reducible oxides. The Fe/N ratio is an important control on nitrate-reducing Fe(II) oxidation processes that occur both in the aquatic environment and in wastewater treatment systems. The response of nitrate reduction, Fe oxidation, and mineral production to different initial Fe/N molar ratios in the presence of Paracoccus denitrificans was investigated in 132 h incubation experiments. A decrease in the nitrate reduction rate at 12 h occurred as the Fe/N ratio increased. Accumulated nitrite concentration at Fe/N ratios of 2–10 peaked at 12–84 h, and then decreased continuously to less than 0.1 mmol/L at the end of incubation. N₂O emission was promoted by high Fe/N ratios. Maximum production of N₂ occurred at a Fe/N ratio of 6, in parallel with the highest mole proportion of N₂ resulting from the reduction of nitrate (81.2%). XRD analysis and sequential extraction demonstrated that the main Fe minerals obtained from Fe(II) oxidation were easily reducible oxides such as ferrihydrite (at Fe/N ratios of 1–2), and easily reducible oxides and reducible oxides (at Fe/N ratios of 3–10). The results suggest that Fe/N ratio potentially plays a critical role in regulating N₂, N₂O emissions and Fe mineral formation in nitrate-reducing Fe(II) oxidation processes.     

Enhanced triallyl isocyanurate (TAIC) degradation through application of an O3/UV process: Performance optimization and degradation pathways

• UV/O₃ process had higher TAIC mineralization rate than O₃ process. • Four possible degradation pathways were proposed during TAIC degradation. • pH impacted oxidation processes with pH of 9 achieving maximum efficiency. • CO₃^2– negatively impacted TAIC degradation while HCO₃^– not. • Cl^– can be radicals scavenger only at high concentration (over 500 mg/L Cl^–). Triallyl isocyanurate (TAIC, C₁₂H₁₅N₃O₃) has featured in wastewater treatment as a refractory organic compound due to the significant production capability and negative environmental impact. TAIC degradation was enhanced when an ozone(O₃)/ultraviolet(UV) process was applied compared with the application of an independent O₃ process. Although 99% of TAIC could be degraded in 5 min during both processes, the O₃/UV process had a 70%mineralization rate that was much higher than that of the independent O₃ process (9%) in 30 min. Four possible degradation pathways were proposed based on the organic compounds of intermediate products identified during TAIC degradation through the application of independent O₃ and O₃/UV processes. pH impacted both the direct and indirect oxidation processes. Acidic and alkaline conditions preferred direct and indirect reactions respectively, with a pH of 9 achieving maximum Total Organic Carbon (TOC) removal. Both CO₃^2– and HCO₃^– decreased TOC removal, however only CO₃^2– negatively impacted TAIC degradation. Effects of Cl^– as a radical scavenger became more marked only at high concentrations (over 500 mg/L Cl^–). Particulate and suspended matter could hinder the transmission of ultraviolet light and reduce the production of HO· accordingly.     

Forward osmosis coupled with lime-soda ash softening for volume minimization of reverse osmosis concentrate and CaCO3 recovery: A case study on the coal chemical industry

• Forward osmosis (FO) coupled with chemical softening for CCI ROC minimization • Effective removal of scale precursor ions by lime-soda ash softening • Enhanced water recovery from 54% to 86% by mitigation of FO membrane scaling • High-purity CaCO₃ was recovered from the softening sludge • Membrane cleaning efficiency of 88.5% was obtained by EDTA for softened ROC Reverse osmosis (RO) is frequently used for water reclamation from treated wastewater or desalination plants. The RO concentrate (ROC) produced from the coal chemical industry (CCI) generally contains refractory organic pollutants and extremely high-concentration inorganic salts with a dissolved solids content of more than 20 g/L contributed by inorganic ions, such as Na⁺, Ca²⁺, Mg²⁺, Cl⁻, and SO₄²⁻. To address this issue, in this study, we focused on coupling forward osmosis (FO) with chemical softening (FO-CS) for the volume minimization of CCI ROC and the recovery of valuable resources in the form of CaCO₃. In the case of the real raw CCI ROC, softening treatment by lime-soda ash was shown to effectively remove Ca²⁺/Ba²⁺ (>98.5%) and Mg²⁺/Sr²⁺/Si (>80%), as well as significantly mitigate membrane scaling during FO. The softened ROC and raw ROC corresponded to a maximum water recovery of 86% and 54%, respectively. During cyclic FO tests (4 × 10 h), a 27% decline in the water flux was observed for raw ROC, whereas only 4% was observed for softened ROC. The cleaning efficiency using EDTA was also found to be considerably higher for softened ROC (88.5%) than that for raw ROC (49.0%). In addition, CaCO₃ (92.2% purity) was recovered from the softening sludge with an average yield of 5.6 kg/m³ treated ROC. This study provides a proof-of-concept demonstration of the FO-CS coupling process for ROC volume minimization and valuable resources recovery, which makes the treatment of CCI ROC more efficient and more economical.     

Reutilize tire in microbial fuel cell for enhancing the nitrogen removal of the anammox process coupled with iron-carbon micro-electrolysis

• MFC promoted the nitrogen removal of anammox with Fe-C micro-electrolysis. • Reutilize pyrolysis waste tire as micro-electrolysis and electrode materials. • Total nitrogen removal efficiency of modified MFC increased to 85.00%. • Candidatus kuenenia and SM1A02 were major genera responsible for nitrogen removal. In this study, microbial fuel cells (MFCs) were explored to promote the nitrogen removal performance of combined anaerobic ammonium oxidation (anammox) and Fe-C micro-electrolysis (CAE) systems. The average total nitrogen (TN) removal efficiency of the modified MFC system was 85.00%, while that of the anammox system was 62.16%. Additionally, the effective operation time of this system increased from six (CAE system alone) to over 50 days, significantly promoting TN removal. The enhanced performance could be attributed to the electron transferred from the anode to the cathode, which aided in reducing nitrate/nitrite in denitrification. The H⁺ released through the proton exchange membrane caused a decrease in the pH, facilitating Fe corrosion. The pyrolyzed waste tire used as the cathode could immobilize microorganisms, enhance electron transport, and produce a natural Fe-C micro-electrolysis system. According to the microbial community analysis, Candidatus kuenenia was the major genus involved in the anammox process. Furthermore, the SM1A02 genus exhibited the highest abundance and was enriched the fastest, and could be a novel potential strain that aids the anammox process.     

Fungal diversity and its mechanism of community shaping in the milieu of sanitary landfill

• Ascomycota was the predominant phylum in sanitary landfill fungal communities. • Saprophytic fungi may be of special importance in landfill ecology. • Both richness and diversity of fungal community were lower in leachate than refuse. • Physical habitat partly contributed to the geographic variance of fungal community. • NO₃⁻ was considered the most significant abiotic factor shaping fungal community. Land filling is the main method to dispose municipal solid waste in China. During the decomposition of organic waste in landfills, fungi play an important role in organic carbon degradation and nitrogen cycling. However, fungal composition and potential functions in landfill have not yet been characterized. In this study, refuse and leachate samples with different areas and depths were taken from a large sanitary landfill in Beijing to identify fungal communities in landfills. In high-throughput sequencing of ITS region, 474 operational taxonomic units (OTUs) were obtained from landfill samples with a cutoff level of 3% and a sequencing depth of 19962. The results indicates that Ascomycota, with the average relative abundance of 84.9%, was the predominant phylum in landfill fungal communities. At the genus level, Family Hypocreaceae unclassified (15.7%), Fusarium (9.9%) and Aspergillus (8.3%) were the most abundant fungi found in the landfill and most of them are of saprotrophic lifestyle, which plays a big role in nutrient cycling in ecosystem. Fungi existed both in landfilled refuse and leachate while both the richness and evenness of fungal communities were higher in the former. In addition, fungal communities in landfilled refuse presented geographic variances, which could be partly attributed to physical habitat properties (pH, dissolved organic carbon, volatile solid, NH₄⁺, NO₂⁻ and NO₃⁻), while NO₃⁻ was considered the most significant factor (p<0.05) in shaping fungal community.     

Ammonia removal from low-strength municipal wastewater by powdered resin combined with simultaneous recovery as struvite

• Powdered resin was employed for ammonia recovery from municipal wastewater. • Powdered resin achievedefficient ammonia removal under various working conditions. • Co-existing cations indicated competitive adsorption of ammonia. • Ammonia was recoveredby two-stage crystallization coupled with ion exchange. Low-strength municipal wastewater is considered to be a recoverable nutrient resource with economic and environmental benefits. Thus, various technologies for nutrient removal and recovery have been developed. In this paper, powdered ion exchange resin was employed for ammonia removal and recovery from imitated low-strength municipal wastewater. The effects of various working conditions (powdered resin dosage, initial concentration, and pH value) were studied in batch experiments to investigate the feasibility of the approach and to achieve performance optimization. The maximum adsorption capacity determined by the Langmuir model was 44.39 mg/g, which is comparable to traditional ion exchange resin. Further, the effects of co-existing cations (Ca²⁺, Mg²⁺, K⁺) were studied. Based on the above experiments, recovery of ammonia as struvite was successfully achieved by a proposed two-stage crystallization process coupled with a powdered resin ion exchange process. Scanning electron microscopy (SEM) and X-ray diffractometry (XRD) results revealed that struvite crystals were successfully gained in alkaline conditions (pH= 10). This research demonstrates that a powdered resin and two-stage crystallization process provide an innovative and promising means for highly efficient and easy recovery from low-strength municipal wastewater.     

Persistent free radicals in humin under redox conditions and their impact in transforming polycyclic aromatic hydrocarbons

• Regulation of redox conditions promotes the generation of free radicals on HM. • HM-PFRs can be fractionated into active and inactive types depending on stability. • The newly produced PFRs readily release electrons to oxygen and generate ROS. • PFR-induced ROS mediate the transformation of organic contaminants adsorbed on HM. The role of humic substance-associated persistent free radicals (PFRs) in the fate of organic contaminants under various redox conditions remains unknown. This study examined the characterization of original metal-free peat humin (HM), and HM treated with varying concentrations of H₂O₂ and L-ascorbic acid (VC) (assigned as H₂O₂-HM and VC-HM). The concentration of PFRs in HM increased with the addition of VC/H₂O₂ at concentrations less than 0.08 M. The evolution of PFRs in HM under different environmental conditions (e.g., oxic/anoxic and humidity) was investigated. Two types of PFRs were detected in HM: a relatively stable radical existed in the original sample, and the other type, which was generated by redox treatments, was relatively unstable. The spin densities of VC/H₂O₂-HM readily returned to the original value under relatively high humidity and oxic conditions. During this process, the HM-associated “unstable” free radicals released an electron to O₂, inducing the formation of reactive oxygen species (ROS, i.e., ^•OH and ^•O₂⁻). The generated ROS promoted the degradation of polycyclic aromatic hydrocarbons based on the radical quenching measurements. The transformation rates followed the order naphthalene>phenanthrene>anthracene>benzo[a]pyrene. Our results provide valuable insight into the HM-induced transformation of organic contaminants under natural conditions.     

Rapid and long-effective removal of broad-spectrum pollutants from aqueous system by ZVI/oxidants

• The coupling of oxidants with ZVI overcome the impedance of ZVI passive layer. • ZVI/oxidants system achieved fast and long-effective removal of contaminants. • Multiple mechanisms are involved in contaminants removal by ZVI/oxidant system. • ZVI/Oxidants did not change the reducing property of ORP in the fixed-bed system. Zero-valent iron (ZVI) technology has recently gained significant interest in the efficient sequestration of a wide variety of contaminants. However, surface passivation of ZVI because of its intrinsic passive layer would lead to the inferior reactivity of ZVI and its lower efficacy in contaminant removal. Therefore, to activate the ZVI surface cheaply, continuously, and efficiently is an important challenge that ZVI technology must overcome before its wide-scale application. To date, several physical and chemical approaches have been extensively applied to increase the reactivity of the ZVI surface toward the elimination of broad-spectrum pollutants. Nevertheless, these techniques have several limitations such as low efficacy, narrow working pH, eco-toxicity, and high installation cost. The objective of this mini-review paper is to identify the critical role of oxygen in determining the reactivity of ZVI toward contaminant removal. Subsequently, the effect of three typical oxidants (H₂O₂, KMnO₄, and NaClO) on broad-spectrum contaminants removal by ZVI has been documented and discussed. The reaction mechanism and sequestration efficacies of the ZVI/oxidant system were evaluated and reviewed. The technical basis of the ZVI/oxidant approach is based on the half-reaction of the cathodic reduction of the oxidants. The oxidants commonly used in the water treatment industry, i.e., NaClO, O₃, and H₂O₂, can be served as an ideal coupling electron receptor. With the combination of these oxidants, the surface corrosion of ZVI can be continuously driven. The ZVI/oxidants technology has been compared with other conventional technologies and conclusions have been drawn.     

Enhanced hydrogen production in microbial electrolysis through strategies of carbon recovery from alkaline/thermal treated sludge

• High hydrogen yield is recovered from thermal-alkaline pretreated sludge. • Separating SFL by centrifugation is better than filtration for hydrogen recovery. • The cascaded bioconversion of complex substrates in MECs are studied. • Energy and electron efficiency related to substrate conversion are evaluated. The aim of this study was to investigate the biohydrogen production from thermal (T), alkaline (A) or thermal-alkaline (TA) pretreated sludge fermentation liquid (SFL) in a microbial electrolysis cells (MECs) without buffer addition. Highest hydrogen yield of 36.87±4.36 mgH₂/gVSS (0.026 m³/kg COD) was achieved in TA pretreated SFL separated by centrifugation, which was 5.12, 2.35 and 43.25 times higher than that of individual alkaline, thermal pretreatment and raw sludge, respectively. Separating SFL from sludge by centrifugation eliminated the negative effects of particulate matters, was more conducive for hydrogen production than filtration. The accumulated short chain fatty acid (SCFAs) after pretreatments were the main substrates for MEC hydrogen production. The maximum utilization ratio of acetic acid, propionic acid and n-butyric acid was 93.69%, 90.72% and 91.85%, respectively. These results revealed that pretreated WAS was highly efficient to stimulate the accumulation of SCFAs. And the characteristics and cascade bioconversion of complex substrates were the main factor that determined the energy efficiency and hydrogen conversion rate of MECs.     

Precise regulation of acid pretreatment for red mud SCR catalyst: Targeting on optimizing the acidity and reducibility

• The optimum SCR activity was realized by tuning the acid pretreatment. • Optimized catalysts showed NO_x conversion above 90%. • The NH₃ and NO adsorption capacity of Al-O₃-Fe is stronger than Fe-O₃-Fe. • The formation of almandine consumes Fe³⁺ and Al³⁺ and weakens their interaction. Red mud (RM), as an alkaline waste, was recently proved to be a promising substitute for the SCR catalyst. Dealkalization could improve the acidity and reducibility of red mud, which were critical for SCR reaction. However, the dealkalization effect depended on the reaction between acid solution and red mud. In this study, we realized the directional control of the chemical state of active sites through tuning the acid pretreatment (dealkalization) process. The pretreatment endpoint was controlled at pH values of 3–5 with diluted nitric acid. When the pH values of red mud were 3 and 5 (CRM-3 and CRM-5), activated catalysts showed NO_x conversion above 90% at 275°C–475°C. The high initial reaction rate, Ce³⁺/(Ce³⁺ + Ce⁴⁺) ratio, and surface acidity accounted for the excellent SCR performance of CRM-5 catalyst. Meanwhile, more Fe³⁺ on the CRM-3 surface improved the NH₃ adsorption. There was a strong interaction between Al and Fe in both CRM-5 and CRM-3 catalysts. DFT results showed that the adsorption capacity of the Al-O₃-Fe for NH₃ and NO is stronger than that of Fe-O₃-Fe, which enhanced the NO_x conversion of the catalyst. However, the almandine was formed in CRM-4, consumed part of Fe³⁺ and Al³⁺, and the interaction between Al and Fe was weakened. Also, deposited almandine on the catalyst surface covered the active sites, thus leading to lower NH₃-SCR activity.     

Degradation of refractory organics in concentrated leachate by the Fenton process: Central composite design for process optimization

• 90% total COD, 95.3% inert COD and 97.2% UV₂₅₄ were removed. • High R² values (over 95%) for all responses were obtained with CCD. • Operational cost was calculated to be 0.238 €/g COD_removed for total COD removal. • Fenton oxidation was highly-efficient method for inert COD removal. • BOD₅/COD ratio of leachate concentrate raised from 0.04 to 0.4. The primary aim of this study is inert COD removal from leachate nanofiltration concentrate because of its high concentration of resistant organic pollutants. Within this framework, this study focuses on the treatability of leachate nanofiltration concentrate through Fenton oxidation and optimization of process parameters to reach the maximum pollutant removal by using response surface methodology (RSM). Initial pH, Fe²⁺ concentration, H₂O₂/Fe²⁺ molar ratio and oxidation time are selected as the independent variables, whereas total COD, color, inert COD and UV₂₅₄ removal are selected as the responses. According to the ANOVA results, the R² values of all responses are found to be over 95%. Under the optimum conditions determined by the model (pH: 3.99, Fe²⁺: 150 mmol/L, H₂O₂/Fe²⁺: 3.27 and oxidation time: 84.8 min), the maximum COD removal efficiency is determined as 91.4% by the model. The color, inert COD and UV₂₅₄ removal efficiencies are determined to be 99.9%, 97.2% and 99.5%, respectively, by the model, whereas the total COD, color, inert COD and UV₂₅₄ removal efficiencies are found respectively to be 90%, 96.5%, 95.3% and 97.2%, experimentally under the optimum operating conditions. The Fenton process improves the biodegradability of the leachate NF concentrate, increasing the BOD₅/COD ratio from the value of 0.04 to the value of 0.4. The operational cost of the process is calculated to be 0.238 €/g COD_removed. The results indicate that the Fenton oxidation process is an efficient and economical technology in improvement of the biological degradability of leachate nanofiltration concentrate and in removal of resistant organic pollutants.     

Membrane-based treatment of shale oil and gas wastewater: The current state of knowledge

• Shale oil and gas production generates wastewater with complex composition. • Membrane technologies emerged for the treatment of shale oil and gas wastewater. • Membrane technologies should tolerate high TDS and consume low primary energy. • Pretreatment is a key component of integrated wastewater treatment systems. • Full-scale implementation of membrane technologies is highly desirable. Shale oil and gas exploitation not only consumes substantial amounts of freshwater but also generates large quantities of hazardous wastewater. Tremendous research efforts have been invested in developing membrane-based technologies for the treatment of shale oil and gas wastewater. Despite their success at the laboratory scale, membrane processes have not been implemented at full scale in the oil and gas fields. In this article, we analyze the growing demands of wastewater treatment in shale oil and gas production, and then critically review the current stage of membrane technologies applied to the treatment of shale oil and gas wastewater. We focus on the unique niche of those technologies due to their advantages and limitations, and use mechanical vapor compression as the benchmark for comparison. We also highlight the importance of pretreatment as a key component of integrated treatment trains, in order to improve the performance of downstream membrane processes and water product quality. We emphasize the lack of sufficient efforts to scale up existing membrane technologies, and suggest that a stronger collaboration between academia and industry is of paramount importance to translate membrane technologies developed in the laboratory to the practical applications by the shale oil and gas industry.     

Using loose nanofiltration membrane for lake water treatment: A pilot study

• A pilot study was conducted for drinking water treatment using loose NF membranes. • The membranes had very high rejection of NOM and medium rejection of Ca²⁺/Mg²⁺. • Organic fouling was dominant and contribution of inorganic fouling was substantial. • Both organic and inorganic fouling had spatial non-uniformity on membrane surface. • Applying EDTA at basic conditions was effective in removing membrane fouling. Nanofiltration (NF) using loose membranes has a high application potential for advanced treatment of drinking water by selectively removing contaminants from the water, while membrane fouling remains one of the biggest problems of the process. This paper reported a seven-month pilot study of using a loose NF membrane to treat a sand filtration effluent which had a relatively high turbidity (~0.4 NTU) and high concentrations of organic matter (up to 5 mg/L as TOC), hardness and sulfate. Results showed that the membrane demonstrated a high rejection of TOC (by>90%) and a moderately high rejection of two pesticides (54%–82%) while a moderate rejection of both calcium and magnesium (~45%) and a low rejection of total dissolved solids (~27%). The membrane elements suffered from severe membrane fouling, with the membrane permeance decreased by 70% after 85 days operation. The membrane fouling was dominated by organic fouling, while biological fouling was moderate. Inorganic fouling was mainly caused by deposition of aluminum-bearing substances. Though inorganic foulants were minor contents on membrane, their contribution to overall membrane fouling was substantial. Membrane fouling was not uniform on membrane. While contents of organic and inorganic foulants were the highest at the inlet and outlet region, respectively, the severity of membrane fouling increased from the inlet to the outlet region of membrane element with a difference higher than 30%. While alkaline cleaning was not effective in removing the membrane foulants, the use of ethylenediamine tetraacetate (EDTA) at alkaline conditions could effectively restore the membrane permeance.     

Water-level based discrete integrated dynamic control to regulate the flow for sewer-WWTP operation

• A model-free sewer-WWTP integrated control was proposed. • A dynamic discrete control based on the water level was developed. • The approach could improve the sewer operation against flow fluctuation. • The approach could increase transport capacity and enhance pump efficiency. This study aims to propose a multi-point integrated real-time control method based on discrete dynamic water level variations, which can be realized only based on the programmable logic controller (PLC) system without using a complex mathematical model. A discretized water level control model was developed to conduct the real-time control based on data-automation. It combines the upstream pumping stations and the downstream influent pumping systems of wastewater treatment plant (WWTP). The discretized water level control method can regulate dynamic wastewater pumping flow of pumps following the dynamic water level variation in the sewer system. This control method has been successfully applied in practical integrated operations of sewer-WWTP following the sensitive flow disturbances of the sewer system. The operational results showed that the control method could provide a more stabilized regulate pumping flow for treatment process; it can also reduce the occurrence risk of combined sewer overflow (CSO) during heavy rainfall events by increasing transport capacity of pumping station and influent flow in WWTP, which takes full advantage of storage space in the sewer system.     

Catalytic oxidation of o-chlorophenol over Co2XAl (X= Co,Mg, Ca,Ni) hydrotalcite-derived mixed oxide catalysts

• Superior catalytic activity observed for o-chlorophenol oxidation on Co₂MgAlO. • The reducibility, oxygen species and basicity influenced catalytic activity. • The organic by-products were generated in o-chlorophenol catalytic oxidation. A cobalt-based hydrotalcite-like compound was prepared using a constant-pH coprecipitation method. Cobalt-transition metal oxides (Co₂XAlO, X= Co, Mg, Ca and Ni) were investigated for the deep catalytic oxidation of o-chlorophenol as a typical heteroatom contaminant containing chlorine atoms. The partial substitution of Co by Mg, Ca or Ni in the mixed oxide can promote the catalytic oxidation of o-chlorophenol. The Co₂MgAlO catalyst presented the best catalytic activity, and could maintain 90% o-chlorophenol conversion at 167.1°C, compared only 27% conversion for the Co₃AlO catalyst. The results demonstrated that the high activity could be attributed to its increased low-temperature reducibility, rich active oxygen species and excellent oxygen mobility. In the existence of acid and base sites, catalysts with strong basicity also showed preferred activity. The organic by-products generated during the o-chlorophenol catalytic oxidation over Co₂MgAlO catalyst included carbon tetrachloride, trichloroethylene, 2,4-dichlorophenol, and 2,6-dichloro-p-benzoquinon, et al. This work provides a facile method for the preparation of Co-based composite oxide catalysts, which represent promising candidates for typical chlorinated and oxygenated volatile organic compounds.     

Effects of hydraulic retention time on net present value and performance in a membrane bioreactor treating antibiotic production wastewater

• The membrane bioreactor cost decreased by 38.2% by decreasing HRT from 72 h to 36 h. • Capital and operation costs contributed 62.1% and 37.9% to decreased costs. • The membrane bioreactor is 32.6% cheaper than the oxidation ditch for treatment. • The effluent COD also improved from 709.93±62.75 mg/L to 280±17.32 mg/L. • Further treatment also benefited from lower pretreatment investment. A cost sensitivity analysis was performed for an industrial membrane bioreactor to quantify the effects of hydraulic retention times and related operational parameters on cost. Different hydraulic retention times (72–24 h) were subjected to a flat-sheet membrane bioreactor updated from an existing 72 h oxidation ditch treating antibiotic production wastewater. Field experimental data from the membrane bioreactor, both full-scale (500 m³/d) and pilot (1.0 m³/d), were used to calculate the net present value (NPV), incorporating both capital expenditure (CAPEX) and operating expenditure. The results showed that the tank cost was estimated above membrane cost in the membrane bioreactor. The decreased hydraulic retention time from 72 to 36 h reduced the NPV by 38.2%, where capital expenditure contributed 24.2% more than operational expenditure. Tank construction cost was decisive in determining the net present value contributed 62.1% to the capital expenditure. The membrane bioreactor has the advantage of a longer lifespan flat-sheet membrane, while flux decline was tolerable. The antibiotics decreased to 1.87±0.33 mg/L in the MBR effluent. The upgrade to the membrane bioreactor also benefited further treatments by 10.1%–44.7% lower direct investment.     

Ammonia and phosphorus removal from agricultural runoff using cash crop waste-derived biochars

• Orange tree residuals biochar had a better ability to adsorb ammonia. • Modified tea tree residuals biochar had a stronger ability to remove phosphorus. • Partially-modified biochar could remove ammonia and phosphorus at the same time. • The real runoff experiment showed an ammonia nitrogen removal rate of about 80%. • The removal rate of total phosphorus in real runoff experiment was about 95%. Adsorption of biochars (BC) produced from cash crop residuals is an economical and practical technology for removing nutrients from agricultural runoff. In this study, BC made of orange tree trunks and tea tree twigs from the Laoguanhe Basin were produced and modified by aluminum chloride (Al-modified) and ferric sulfate solutions (Fe-modified) under various pyrolysis temperatures (200°C–600°C) and residence times (2–5 h). All produced and modified BC were further analyzed for their abilities to adsorb ammonia and phosphorus with initial concentrations of 10–40 mg/L and 4–12 mg/L, respectively. Fe-modified Tea Tree BC 2h/400°C showed the highest phosphorus adsorption capacity of 0.56 mg/g. Al-modified Orange Tree BC 3h/500°C showed the best performance for ammonia removal with an adsorption capacity of 1.72 mg/g. FTIR characterization showed that P = O bonds were formed after the adsorption of phosphorus by modified BC, N-H bonds were formed after ammonia adsorption. XPS analysis revealed that the key process of ammonia adsorption was the ion exchange between K⁺ and NH₄⁺. Phosphorus adsorption was related to oxidation and interaction between PO₄^3– and Fe³⁺. According to XRD results, ammonia was found in the form of potassium amide, while phosphorus was found in the form of iron hydrogen phosphates. The sorption isotherms showed that the Freundlich equation fits better for phosphorus adsorption, while the Langmuir equation fits better for ammonia adsorption. The simulated runoff infiltration experiment showed that 97.3% of ammonia was removed by Al-modified Orange tree BC 3h/500°C, and 92.9% of phosphorus was removed by Fe-modified Tea tree BC 2h/400°C.