Scrap Iron Filings assisted nitrate and phosphate removal in low C/N waters using mixed microbial culture

• Microbes enhance denitrification under varying DO concentrations and SIF dosages. • Abiotic nitrate reduction rates are proportional to SIF age and dosage. • Over 80% of the simultaneously loaded NO₃⁻-N and PO₄³⁻ is removed biologically. This study focuses on identifying the factors under which mixed microbial seeds assist bio-chemical denitrification when Scrap Iron Filings (SIF) are used as electron donors and adsorbents in low C/N ratio waters. Batch studies were conducted in abiotic and biotic reactors containing fresh and aged SIF under different dissolved oxygen concentrations with NO₃⁻-N and/or PO₄^3- influent(s) and their nitrate/phosphate removal and by-product formations were studied. Batch reactors were seeded with a homogenized mixed microbial inoculum procured from natural sludges which were enriched over 6 months under denitrifying conditions in the presence of SIF. Results indicated that when influent containing 40 mg/L of NO₃⁻-N was treated with 5 g SIF, 79.9% nitrate reduction was observed in 8 days abiotically and 100% removal was accomplished in 20 days when the reactor was seeded. Both abiotic and seeded reactors removed more than 92% PO₄³⁻ under high DO conditions in 12 days. Abiotic and biochemical removal of NO₃⁻-N and abiotic removal of PO₄³⁻ were higher under independent NO₃⁻-N/PO₄³⁻ loading, while 99% PO₄^3- was removed biochemically under combined NO₃⁻-N and PO₄³⁻ loading. This study furthers the understandings of nitrate and phosphate removal in Zero Valent Iron (ZVI) assisted mixed microbial systems to encourage the application of SIF-supported bio-chemical processes in the simultaneous removals of these pollutants.     

Zero-valent manganese nanoparticles coupled with different strong oxidants for thallium removal from wastewater

• Nano zero-valent manganese (nZVMn, Mn⁰) is synthesized via borohydrides reduction. • Mn⁰ combined with persulfate/hypochlorite is effective for Tl removal at pH 6-12. • Mn⁰ can activate persulfate to form hydroxyl and sulfate radicals. • Oxidation-induced precipitation and surface complexation contribute to Tl removal. • Combined Mn⁰-oxidants process is promising in the environmental field. Nano zero-valent manganese (nZVMn, Mn⁰) was prepared through a borohydride reduction method and coupled with different oxidants (persulfate (S₂O₈²⁻), hypochlorite (ClO⁻), or hydrogen peroxide (H₂O₂)) to remove thallium (Tl) from wastewater. The surface of Mn⁰ was readily oxidized to form a core-shell composite (MnO_x@Mn⁰), which consists of Mn⁰ as the inner core and MnO_x (MnO, Mn₂O₃, and Mn₃O₄) as the outer layer. When Mn⁰ was added alone, effective Tl(I) removal was achieved at high pH levels (>12). The Mn⁰-H₂O₂ system was only effective in Tl(I) removal at high pH (>12), while the Mn⁰-S₂O₈²⁻ or Mn⁰-ClO⁻ system had excellent Tl(I) removal (>96%) over a broad pH range (4–12). The Mn⁰-S₂O₈²⁻ oxidation system provided the best resistance to interference from an external organic matrix. The isotherm of Tl(I) removal through the Mn⁰-S₂O₈²⁻ system followed the Freundlich model. The Mn⁰ nanomaterials can activate persulfate to produce sulfate radicals and hydroxyl radicals. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy suggested that oxidation-induced precipitation, surface adsorption, and electrostatic attraction are the main mechanisms for Tl(I) removal resulting from the combination of Mn⁰ and oxidants. Mn⁰ coupled with S₂O₈²⁻/ClO⁻ is a novel and effective technique for Tl(I) removal, and its application in other fields is worthy of further investigation.     

Fermentative hydrogen production from beet sugar factory wastewater treatment in a continuous stirred tank reactor using anaerobic mixed consortia

A low pH, ethanol-type fermentation process was evaluated for wastewater treatment and bio-hydrogen production from acidic beet sugar factory wastewater in a continuous stirred tank reactor (CSTR) with an effective volume of 9.6 L by anaerobic mixed cultures in this present study. After inoculating with aerobic activated sludge and operating at organic loading rate (OLR) of 12 kgCOD?m^-3·d^-1, HRT of 8h, and temperature of 35°C for 28 days, the CSTR achieved stable ethanol-type fermentation. When OLR was further increased to 18 kgCOD?m^-3·d^-1 on the 53rd day, ethanol-type fermentation dominant microflora was enhanced. The liquid fermentation products, including volatile fatty acids (VFAs) and ethanol, stabilized at 1493 mg·L^-1 in the bioreactor. Effluent pH, oxidation-reduction potential (ORP), and alkalinity ranged at 4.1–4.5, -250–(-290) mV, and 230–260 mgCaCO₃?L^-1. The specific hydrogen production rate of anaerobic activated sludge was 0.1 L?gMLVSS^-1·d^-1 and the COD removal efficiency was 45%. The experimental results showed that the CSTR system had good operation stability and microbial activity, which led to high substrate conversion rate and hydrogen production ability.     

Ozonation of the 5-fluorouracil anticancer drug and its prodrug capecitabine: Reaction kinetics,oxidation mechanisms,and residual toxicity

Specific second-order rate constants were determined for 5-FU and CAP with ozone. Reaction sites were confirmed by kinetics, Fukui analysis, and products. The olefin moiety was the main ozone reaction site for 5-FU and CAP. Carboxylic acids comprised most of the residual TOC for 5-FU. Ozonation removed the toxicity associated with 5-FU and products but not CAP. Anticancer drugs (ADs) have been detected in the environment and represent a risk to aquatic organisms, necessitating AD removal in drinking water and wastewater treatment. In this study, ozonation of the most commonly used antimetabolite ADs, namely 5-fluorouracil (5-FU) and its prodrug capecitabine (CAP), was investigated to determine reaction kinetics, oxidation mechanisms, and residual toxicity. The specific second-order rate constants between aqueous ozone and 5-FU, 5-FU⁻, 5-FU²⁻, CAP, and CAP⁻ were determined to be 7.07(±0.11)×10⁴ M⁻¹·s⁻¹, 1.36(±0.06)×10⁶ M⁻¹·s⁻¹, 2.62(±0.17)×10⁷ M⁻¹·s⁻¹, 9.69(±0.08)×10³ M⁻¹·s⁻¹, and 4.28(±0.07)×10⁵ M⁻¹·s⁻¹, respectively; furthermore, the second-order rate constants for ^•OH reaction with 5-FU and CAP at pH 7 were determined to be 1.85(±0.20)×10⁹ M⁻¹·s⁻¹ and 9.95(±0.26)×10⁹ M⁻¹·s⁻¹, respectively. Density functional theory was used to predict the main ozone reaction sites of 5-FU (olefin) and CAP (olefin and deprotonated secondary amine), and these mechanisms were supported by the identified transformation products. Carboxylic acids constituted a majority of the residual organic matter for 5-FU ozonation; however, carboxylic acids and aldehydes were important components of the residual organic matter generated by CAP. Ozone removed the toxicity of 5-FU to Vibrio fischeri, but the residual toxicity of ozonated CAP solutions exhibited an initial increase before subsequent removal. Ultimately, these results suggest that ozone is a suitable technology for treatment of 5-FU and CAP, although the residual toxicity of transformation products must be carefully considered.     

Continuous biohydrogen production from diluted molasses in an anaerobic contact reactor

An anaerobic contact reactor (ACR) system comprising a continuous flow stirred tank reactor (CSTR) with settler to decouple the hydraulic retention time (HRT) from solids retention time (SRT) was developed for fermentative hydrogen production from diluted molasses by mixed microbial cultures. The ACR was operated at various volumetric loading rates (VLRs) of 20–44 kgCOD·m^-3·d^-1 with constant HRT of 6 h under mesophilic conditions of 35°C. The SRT was maintained at about 46–50 h in the system. At the initial VLR of 20 kgCOD·m^-3·d^-1, the hydrogen production rate dropped from 22.6 to 1.58 L·d^-1 as the hydrogen was consumed by the hydrogentrophic methanogen. After increasing the VLR to 28 kgCOD·m^-3·d^-1 and discharging the sludge for 6 consecutive times, the hydrogentrophic methanogens were eliminated, and the hydrogen content reached 36.4%. As the VLR was increased to 44 kgCOD·m^-3·d^-1, the hydrogen production rate and hydrogen yield increased to 42.1 L·d^-1 and 1.40 mol H₂·molglucose-consumed^-1, respectively. The results showed that a stable ethanol-type fermentation that favored hydrogen production in the reactor was thus established with the sludge loading rate (SLR) of 2.0–2.5 kgCOD·kgMLVSS^-1·d^-1. It was found that the ethanol increased more than other liquid fermentation products, and the ethanol/acetic acid (mol/mol) ratio increased from 1.27 to 2.45 when the VLR increased from 28 to 44 kgCOD·m^-3·d^-1, whereas the hydrogen composition decreased from 40.4% to 36.4%. The results suggested that the anaerobic contact reactor was a promising bioprocess for fermentative hydrogen production.     

Application of Fe0/C/Clay ceramics for decoloration of synthetic Acid Red 73 and Reactive Blue 4 wastewater by micro-electrolysis

Dyes are common pollutants in textile wastewaters, and the treatment of the wastewater has now attracted much attention due to its wide application and low biodegradability. In this study, Fe⁰/C/Clay ceramics, a kind of novel micro-electrolysis filler, were sintered and employed in a dynamic micro-electrolysis reactor for synthetic Acid Red 73 (AR73) and Reactive Blue 4 (RB4) wastewater treatment. The effects of influent pH, hydraulic retention time (HRT), and aeration on the decoloration efficiencies of AR73 and RB4 were studied. The optimum conditions for wastewater treatment were: AR73, influent pH of 4, HRT of 2 h and aeration; RB4, influent pH of 5, HRT of 6 h and aeration. Under the optimum conditions, decoloration efficiency of AR73 and RB4 wastewater was 96% and 83%, respectively. Results of UV-vis spectrum scanning demonstrated that the chromophores were broken. Continuous running tests showed that improvement of micro-electrolysis system with Fe⁰/C/Clay ceramics for AR73 and RB4 synthetic wastewater treatment could avoid failure of micro-electrolysis reactor, which indicated great potential for the practical application of the ceramics in the field of actual industrial wastewater treatment.     

Preparation of nZVI embedded modified mesoporous carbon for catalytic persulfate to degradation of reactive black 5

• The MCNZVI is prepared as an interesting material for PS activation. • Graphitized carbon shells facilitate electron transfer from Fe⁰. • The MCNZVI exhibits excellent performance to degrade RB5 by ¹O₂. • The MCNZVI has high stability and reusability in the oxidation system. High-efficiency and cost-effective catalysts with available strategies for persulfate (PS) activation are critical for the complete mineralization of organic contaminants in the environmental remediation and protection fields. A nanoscale zero-valent iron-embedded modified mesoporous carbon (MCNZVI) with a core-shell structure is synthesized using the hydrothermal synthesis method and high-temperature pyrolysis. The results showed that nZVI could be impregnated within mesoporous carbon frameworks with a comparatively high graphitization degree, rich nitrogen doping content, and a large surface area and pore volume. This material was used as a persulfate activator for the oxidation removal of Reactive Black 5 (RB5). The effects of the material dosage, PS concentration, pH, and some inorganic anions (i.e., Cl⁻, SO₄²⁻) on RB5 degradation were then investigated. The highest degradation efficiency (97.3%) of RB5 was achieved via PS (20 mmol/L) activation by the MCNZVI (0.5 g/L). The pseudo-first-order kinetics (k = 2.11 × 10⁻² min⁻¹) in the MCNZVI/PS (0.5 g/L, 20 mmol/L) was greater than 100 times than that in the MCNZVI and PS. The reactive oxygen species (ROS), including ¹O₂, SO₄^·−, HO^·, and ·O₂⁻, were generated by PS activation with the MCNZVI. Singlet oxygen was demonstrated to be the primary ROS responsible for the RB5 degradation. The MCNZVI could be reused and regenerated for recycling. This work provides new insights into PS activation to remove organic contamination.     

Reduction of hexavalent chromium with scrap iron in a fixed bed reactor

The reduction of hexavalent chromium by scrap iron was investigated in continuous long-term fixed bed system. The effects of pH, empty bed contact time (EBCT), and initial Cr(VI) concentration on Cr(VI) reduction were studied. The results showed that the pH, EBCT, and initial Cr(VI) concentration significantly affected the reduction capacity of scrap iron. The reduction capacity of scrap iron were 4.56, 1.51, and 0.57 mg Cr(VI)·g^-1 Fe⁰ at pH 3, 5, and 7 (initial Cr(VI) concentration 4 mg·L^-1, EBCT 2 min, and temperature 25°C), 0.51, 1.51, and 2.85 mg Cr(VI)·g^-1 Fe⁰ at EBCTs of 0.5, 2.0, and 6.0 min (initial Cr(VI) concentration 4 mg·L^-1, pH 5, and temperature 25°C), and 2.99, 1.51, and 1.01 mg Cr(VI)·g^-1 Fe⁰ at influent concentrations of 1, 4, and 8 mg·L^-1 (EBCT 2 min, pH 5, and temperature 25°C), respectively. Fe(total) concentration in the column effluent continuously decreased in time, due to a decrease in time of the iron corrosion rate. The fixed bed reactor can be readily used for the treatment of drinking water containing low amounts of Cr(VI) ions, although the hardness and humic acid in water may shorten the lifetime of the reactor, the reduction capacity of scrap iron still achieved 1.98 mg Cr⁶⁺·g^-1 Fe. Scanning electron microscope equipped with energy dispersion spectrometer and X-ray diffraction were conducted to examine the surface species of the scrap iron before and after its use. In addition to iron oxides and hydroxide species, iron-chromium complex was also observed on the reacted scrap iron.     

Removal of ammonium and nitrate through Anammox and FeS-driven autotrophic denitrification

● Simultaneous NH₄⁺/NO₃^– removal was achieved in the FeS denitrification system ● Anammox coupled FeS denitrification was responsible for NH₄⁺/NO₃^– removal ● Sulfammox, Feammox and Anammox occurred for NH₄⁺ removal ● Thiobacillus, Nitrospira , and Ca. Kuenenia were key functional microorganisms An autotrophic denitrifying bioreactor with iron sulfide (FeS) as the electron donor was operated to remove ammonium (NH₄⁺) and nitrate (NO₃⁻) synergistically from wastewater for more than 298 d. The concentration of FeS greatly affected the removal of NH₄⁺/NO₃⁻. Additionally, a low hydraulic retention time worsened the removal efficiency of NH₄⁺/NO₃⁻. When the hydraulic retention time was 12 h, the optimal removal was achieved with NH₄⁺ and NO₃⁻ removal percentages both above 88%, and the corresponding nitrogen removal loading rates of NH₄⁺ and NO₃⁻ were 49.1 and 44.0 mg/(L·d), respectively. The removal of NH₄⁺ mainly occurred in the bottom section of the bioreactor through sulfate/ferric reducing anaerobic ammonium oxidation (Sulfammox/Feammox), nitrification, and anaerobic ammonium oxidation (Anammox) by functional microbes such as Nitrospira, Nitrosomonas, and Candidatus Kuenenia. Meanwhile, NO₃⁻ was mainly removed in the middle and upper sections of the bioreactor through autotrophic denitrification by Ferritrophicum, Thiobacillus, Rhodanobacter, and Pseudomonas, which possessed complete denitrification-related genes with high relative abundances.     

Biosorption of Cr(III) from aqueous solution by freeze-dried activated sludge: Equilibrium,kinetic and thermodynamic studies

Batch biosorption experiments were conducted to remove Cr(III) from aqueous solutions using activated sludge from a sewage treatment plant. An investigation was conducted on the effects of the initial pH, contact time, temperature, and initial Cr(III) concentration in the biosorption process. The results revealed that the activated sludge exhibited the highest Cr(III) uptake capacity (120 mg·g⁻¹) at 45°C, initial pH of 4, and initial Cr(III) concentration of 100 mg·L⁻¹. The biosorption results obtained at various temperatures showed that the biosorption pattern accurately followed the Langmuir model. The calculated thermodynamic parameters, ΔG^o (−0.8– −4.58 kJ·mol⁻¹), ΔH^o (15.6–44.4 kJ·mol⁻¹), and ΔS^o (0.06–0.15 kJ·mol⁻¹·K⁻¹) clearly indicated that the biosorption process was feasible, spontaneous, endothermic, and physical. The pseudo first-order and second-order kinetic models were adopted to describe the experimental data, which revealed that the Cr(III) biosorption process conformed to the second-order rate expression and the biosorption rate constants decreased with increasing Cr(III) concentration. The analysis of the values of biosorption activation energy (E_a = −7 kJ·mol⁻¹) and the intra-particle diffusion model demonstrated that Cr(III) biosorption was film-diffusion-controlled.     

Mass-transfer processes of chromium(VI) adsorption onto guava seeds

The chromium(VI) biosorption onto guava seeds, as an alternative method for Cr⁶⁺ removal from aqueous solutions, was investigated. The parameters affecting kinetics and equilibrium of Cr⁶⁺ adsorption onto guava seeds were studied. An external mass-transfer diffusion coefficient k and intra-particle diffusion coefficient k_i were determined to measure the rate-limiting step of adsorption. A single external mass-transfer diffusion model and intra-particle diffusion models were used. The effects of initial pH, sorbent mass, and initial Cr⁶⁺ concentrations on mass-transfer coefficients were investigated. The external mass-transfer coefficient has an average value of 7.2×10^-3 cm s^-1, while the intra-particle mass-transfer diffusion coefficient was 0.34 mg g^-1 min^-0.5. This indicates that external diffusion to the guava seeds surface and intra-particle diffusion are both involved in the sorption process. The isotherm equilibrium data were well fitted by the Langmuir and Freundlich models with an average correlation coefficient R²=0.98. The maximum removal of Cr⁶⁺ was obtained at pH 1 (about 100% for adsorbent dose of 15 g l^-1 and 25 mg l^-1 initial concentration of Cr⁶⁺). The results indicated that the guava seeds exhibit acceptable sorption capacity.     

Partial anammox achieved in full scale biofilm process for typical domestic wastewater treatment

• A full scale biofilm process was developed for typical domestic wastewater treatment. • The HRT was 8 h and secondary sedimentation tank was omitted. • Candidatus Brocadia were enriched in the HBR with an abundance of 2.89%. • Anammox enabled a stable ammonium removal of ~15% in the anoxic zone. The slow initiation of anammox for treating typical domestic wastewater and the relatively high footprint of wastewater treatment infrastructures are major concerns for practical wastewater treatment systems. Herein, a 300 m³/d hybrid biofilm reactor (HBR) process was developed and operated with a short hydraulic retention time (HRT) of 8 h. The analysis of the bacterial community demonstrated that anammox were enriched in the anoxic zone of the HBR process. The percentage abundance of Candidatus Brocadia in the total bacterial community of the anoxic zone increased from 0 at Day 1 to 0.33% at Day 130 and then to 2.89% at Day 213. Based upon the activity of anammox bacteria, the removal of ammonia nitrogen (NH₄⁺-N) in the anoxic zone was approximately 15%. This showed that the nitrogen transformation pathway was enhanced in the HBR system through partial anammox process in the anoxic zone. The final effluent contained 12 mg/L chemical oxygen demand (COD), 0.662 mg/L NH₄⁺-N, 7.2 mg/L total nitrogen (TN), and 6 mg/L SS, indicating the effectiveness of the HBR process for treating real domestic wastewater.     

Preparation of a permanent magnetic hypercrosslinked resin and assessment of its ability to remove organic micropollutants from drinking water

A rapid and effective method based on a novel permanent magnetic hypercrosslinked resin W150 was proposed for the removal of organic micropollutants in drinking water. W150 was prepared by suspension and post-crosslinking reaction and found to possess a high specific surface area of 1149.7 m²·g^-1, a small particle size of 50 μm to 100 μm, and a saturation magnetization as high as 8 emu·g^-1. W150 was used to eliminate nitrofurazone (NFZ) and oxytetracycline (OTC) from drinking water compared with commercial adsorbents XAD-4 and F400D. The adsorption kinetics of NFZ and OTC onto the three adsorbents well fitted the pseudo-second-order equation (r>0.972), and the adsorption isotherms were all well described by the Freundlich equation (r>0.851). Results showed that the reduction in adsorbent size and the enlargement in sorbent pores both accelerated adsorption. Moreover, the effect of particle size on adsorption was more significant than that of pore width. Given that the smallest particle size and the highest specific surface area were possessed by W150, it had the fastest adsorption kinetics and largest adsorption capacity for NFZ (180 mg·g^-1) and OTC (200 mg·g^-1). For the adsorbents with dominant micropores, the sorption of large-sized adsorbates decreased because of the inaccessible micropores. The solution pH and ionic strength also influenced adsorption.     

Deciphering the effect of sodium dodecylbenzene sulfonate on up-flow anaerobic sludge blanket treatment of synthetic sulfate-containing wastewater

• UASB reactor can work efficiently with high COD/SO₄^2- ratios when SDBS exists. • Outcome of the competition between SRB and MPA was affected by SDBS. • Presence of SDBS makes methanogens with H₂/CO₂ as a substrate dominant. • Microbial diversity decreases in the presence of SDBS. In this study, the effects of organic sulfur on anaerobic biological processes were investigated by operating two up-flow anaerobic sludge blanket (UASB) reactors with sodium dodecylbenzene sulfonate (SDBS) as a representative of organic sulfur. The results indicated that the specific methanogenic activity (SMA) and chemical oxygen demand (COD) removal efficiency of R2 (with SDBS added) were higher than those of R1 (without SDBS) when the COD/SO₄²⁻ ratio was above 5.0. However, when the COD/SO₄²⁻ ratio was lower than 5.0, the sulfate reduction efficiency of R2 was higher than that of R1. These results and the observed SDBS transformation efficiency in anaerobic reactors indicate that low concentrations of SDBS accelerate methane production and the continuous accumulation of SDBS does not weaken the reduction of sulfate. Similarly, the calculated electron flux for a COD/SO₄²⁻ ratio of 1.0 indicates that the utilization intensity of electrons by sulfate-reducing bacteria (SRB) in R2 was 36.48% higher than that of SRB in R1 and exceeded that of methane-producing archaea (MPA) under identical working conditions. Moreover, the addition of SDBS in R2 made sulfidogenesis the dominant reaction at low COD/SO₄²⁻, and Methanobacterium and Methanobrevibacter with H₂/CO₂ as the substrate and Desulfomicrobium were the dominant MPA and SRB, respectively. However, methanogenesis was still the dominant reaction in R1, and Methanosaeta with acetic acid as the substrate and Desulfovibrio were the dominant MPA and SRB, respectively.     

Fe2O3-CeO2-Bi2O3/γ-Al2O3 catalyst in the catalytic wet air oxidation (CWAO) of cationic red GTL under mild reaction conditions

Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃, an environmental friendly material, was investigated. The catalyst exhibited good catalytic performance in the CWAO of cationic red GTL. The apparent activation energy for the reaction was 79 kJ·mol⁻¹. HO₂· and O₂·⁻ appeared as the main reactive species in the reaction. The Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃ catalyst, a novel environmental-friendly material, was used to investigate the catalytic wet air oxidation (CWAO) of cationic red GTL under mild operating conditions in a batch reactor. The catalyst was prepared by wet impregnation, and characterized by special surface area (BET measurement), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃ catalyst exhibited good catalytic activity and stability in the CWAO under atmosphere pressure. The effect of the reaction conditions (catalyst loading, degradation temperature, solution concentration and initial solution pH value) was studied. The result showed that the decolorization efficiency of cationic red GTL was improved with increasing the initial solution pH value and the degradation temperature. The apparent activation energy for the reaction was 79 kJ·mol⁻¹. Hydroperoxy radicals (HO₂·) and superoxide radicals (O₂⁻·) appeared as the main reactive species upon the CWAO of cationic red GTL.     

Concurrent adsorption and reduction of chromium(VI) to chromium(III) using nitrogen-doped porous carbon adsorbent derived from loofah sponge

• A high-efficiency N-doped porous carbon adsorbent for Cr(VI) was synthesized. • The maximum adsorption capacity of Cr(VI) reached up to 285.71 mg/g at 318K. • The potential mechanism for Cr(VI) adsorption by NHPC was put forward. • DFT analyzed the adsorption energy and interaction between NHPC and Cr(VI). To develop highly effective adsorbents for chromium removal, a nitrogen-doped biomass-derived carbon (NHPC) was synthesized via direct carbonation of loofah sponge followed by alkali activation and doping modification. NHPC possessed a hierarchical micro-/mesoporous lamellar structure with nitrogen-containing functional groups (1.33 at%), specific surface area (1792.47 m²/g), and pore volume (1.18 cm³/g). NHPC exhibited a higher Cr(VI) adsorption affinity than the HPC (without nitrogen doping) or the pristine loofah sponge carbon (LSC) did. The influence of process parameters, including pH, dosage, time, temperature, and Cr(VI) concentration, on Cr(VI) adsorption by NHPC were evaluated. The Cr(VI) adsorption kinetics matched with the pseudo-second-order model (R²≥0.9983). The Cr(VI) adsorption isotherm was fitted with the Langmuir isotherm model, which indicated the maximum Cr(VI) adsorption capacities: 227.27, 238.10, and 285.71 mg/g at 298K, 308K, and 318K, respectively. The model analysis also indicated that adsorption of Cr(VI) on NHPC was a spontaneous, endothermal, and entropy-increasing process. The Cr(VI) adsorption process potentially involved mixed reductive and adsorbed mechanism. Furthermore, computational chemistry calculations revealed that the adsorption energy between NHPC and Cr(VI) (−0.84 eV) was lower than that of HPC (−0.51 eV), suggesting that nitrogen doping could greatly enhance the interaction between NHPC and Cr(VI).     

Methanation and chemolitrophic nitrogen removal by an anaerobic membrane bioreactor coupled partial nitrification and Anammox

● Efficient carbon methanation and nitrogen removal was achieved in AnMBR-PN/A system. ● AOB outcompeted NOB in PN section by limiting aeration and shortening SRT. ● The moderate residual organic matter of PN section triggered PD in anammox unit. ● AnAOB located at the bottom of UASB played an important role in nitrogen removal. An AnMBR-PN/A system was developed for mainstream sewage treatment. To verify the efficient methanation and subsequent chemolitrophic nitrogen removal, a long-term experiment and analysis of microbial activity were carried out. AnMBR performance was less affected by the change of hydraulic retention time (HRT), which could provide a stable influent for subsequent PN/A units. The COD removal efficiency of AnMBR was > 93% during the experiment, 85.5% of COD could be recovered in form of CH₄. With the HRT of PN/A being shortened from 10 to 6 h, nitrogen removal efficiency (NRE) of PN/A increased from 60.5% to 80.4%, but decreased to 68.8% when the HRT_PN/A further decreased to 4 h. Microbial analysis revealed that the highest specific ammonia oxidation activity (SAOA) and the ratio of SAOA to specific nitrate oxidation activity (SNOA) provide stable NO₂⁻-N/NH₄⁺-N for anammox, and anammox bacteria (mainly identified as Candidatus Brocadia) enriched at the bottom of Anammox-UASB might play an important role in nitrogen removal. In addition, the decrease of COD in Anammox-UASB indicated partial denitrification occurred, which jointly promoted nitrogen removal with anammox.     

Oxidation and biotoxicity assessment of microcystin-LR using different AOPs based on UV,O3 and H2O2

MC-LR removal performances under different AOPs were compared systematically. Higher removal efficiency and synergistic effects were obtained by combined process. The acute biotoxicity raised in different degrees after oxidation. Microcystin-LR attracts attention due to its high toxicity, high concentration and high frequency. The removal characteristics of UV/H₂O₂ and O₃/H₂O₂ advanced oxidation processes and their individual process for MC-LR were investigated and compared in this study. Both the removal efficiencies and rates of MC-LR as well as the biotoxicity of degradation products was analyzed. Results showed that the UV/H₂O₂ process and O₃/H₂O₂ were effective methods to remove MC-LR from water, and they two performed better than UV-, O₃-, H₂O₂-alone processes under the same conditions. The effects of UV intensity, H₂O₂ concentration and O₃ concentration on the removal performance were explored. The synergistic effects between UV and H₂O₂, O₃ and H₂O₂ were observed. UV dosage of 1800 mJ·cm⁻² was required to remove 90% of 100 mg·L⁻¹ MC-LR, which amount significantly decreased to 500 mJ·cm⁻² when 1.7 mg·L⁻¹ H₂O₂ was added. 0.25 mg·L⁻¹ O₃, or 0.125 mg·L⁻¹ O₃ with 1.7 mg·L⁻¹ H₂O₂ was needed to reach 90% removal efficiency. Furthermore, the biotoxicity results about these UV/H₂O₂, O₃/H₂O₂ and O₃-alone processes all present rising trends with oxidation degree of MC-LR. Biotoxicity of solution, equivalent to 0.01 mg·L⁻¹ Zn²⁺, raised to 0.05 mg·L⁻¹ Zn²⁺ after UV/H₂O₂ or O₃/H₂O₂ reaction. This phenomenon may be attributed to the aldehydes and ketones with small molecular weight generated during reaction. Advice about the selection of MC-LR removal methods in real cases was provided.     

Pomegranate husk as an adsorbent in the removal of toxic chromium from wastewater

The use of a new sorbent developed from the husk of pomegranate, a famous fruit in Egypt, for the removal of toxic chromium from aqueous solution has been investigated. The batch experiment was conducted to determine the adsorption capacity of the pomegranate husk. The effects of initial metal concentration (25 and 50 mg l^-1), pH, contact time, and sorbent concentration (2-6 g l^-1) have been studied at room temperature. A strong dependence of the adsorption capacity on pH was observed, the capacity increased as the pH decreased, and the optimum pH value was pH 1.0. Adsorption equilibrium and kinetics were studied with different sorbent and metal concentrations. The adsorption process was fast, and equilibrium was reached within 3 h. The maximum removal was 100% for 25 mg l^-1 of Cr⁶⁺ concentration on 5 g l^-1 pomegranate husk concentration, and the maximum adsorption capacity was 10.59 mg g^-1. The kinetic data were analysed using various kinetic models—pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion equations—and the equilibrium data were tested using several isotherm models, Langmuir, Freundlich, Tempkin, Dubinin-Radushkevich, and Generalized isotherm equations. The Elovich and pseudo-second-order equations provided the greatest accuracy for the kinetic data, while Langmuir and Generalized isotherm models were the closest fit for the equilibrium data. The activation energy of sorption has also been evaluated as 0.236 and 0.707 kJ mol^-1 for 25 and 50 mg l^-1 chromium concentration, respectively.     

Performance of an ANAMMOX reactor treating wastewater generated by antibiotic and starch production processes

A pilot-scale anaerobic ammonia oxidation (ANAMMOX) reactor was used to treat mixed wastewater resulting from a chlortetracycline and starch production process. The results, collected over the course of 272 days, show that the ratio of influent ammonium to nitrite, pH, and temperature can all affect the efficiency of nitrogen removal. The ratio of influent ammonium to nitrite was maintained at about 1:1 at a concentration below 200 mg·L^-1 for both influent ammonium and nitrite. The total nitrogen (TN) loading rate was 0.15–0.30 kgN·m^-3·d^-1, pH remained at 7.8–8.5, and temperature was recorded at 33±1°C. The rate of removal of ammonia, nitrite, and TN were over 90%, 90%, and 80%, and the effluent ammonium, nitrite and TN concentrations were below 50, 30, and 100 mg·L^-1.