Utilization of MSWI fly ash as partial cement or sand substitute with focus on cementing efficiency and health risk assessment

• Washed MSWI fly ash was used as partial cement or sand substitute. • Sand replacing is beneficial for strength, while cement replacement reduces strength. • Cementing efficiency factor and mortar pore structure explain the strength results. • Health risk assessment was conducted for MSWI fly ash blended cement mortar. • CR and HI contributed by different exposures and heavy metals were analyzed. The strength of cement substituted mortar decreases with the increase in fly ash amount, whereas the strength increases when the fly ash is blended as sand substitute. A mortar with highest strength (compressive strength= 30.2 Mpa; flexural strength= 7.0 Mpa) was obtained when the sand replacement ratio was 0.75%. The k value (cementing efficiency) of fly ash varied between 0.36 and 0.15 for the fly ash fraction in binder between 5% and 25%. The k values of fly ash used for sand replacement were all significantly above that used for cement substitution. The macropores assigned to the gaps between particles decreased when the fly ash was used as sand replacement, providing an explanation for the strength enhancement. The waste-extraction procedure (toxicity-sulphuric acid and nitric acid method (HJ/T 299-2007)) was used to evaluate metal leaching, indicating the reuse possibility of fly ash blended mortar. For the mortar with the mass ratio of fly ash to binder of 0.5%, the carcinogenic risks (CR) and non-carcinogenic hazard quotient (HQ) in sensitive scenario for blended mortar utilization were 9.66 × 10^-7 and 0.06, respectively; these results were both lower than the threshold values, showing an acceptable health risk. The CR (9.89 × 10^-5) and HQ (3.89) of the non-sensitive scenario for fly ash treatment exceeded the acceptable threshold values, indicating health risks to onsite workers. The main contributor to the carcinogenic and non-carcinogenic risk is Cr and Cd, respectively. The CR and HQ from inhalation was the main route of heavy metal exposure.     

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.     

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.     

Visible-light-driven heterostructured g-C3N4/Bi-TiO2 floating photocatalyst with enhanced charge carrier separation for photocatalytic inactivation of Microcystis aeruginosa

• Bi doping in TiO₂ enhanced the separation of photo-generated electron-hole. • The performance of photocatalytic degradation of MC-LR was improved. • Coexisting substances have no influence on algal removal performance. • The key reactive oxygen species were h⁺ and ^•OH in the photocatalytic process. The increase in occurrence and severity of cyanobacteria blooms is causing increasing concern; moreover, human and animal health is affected by the toxic effects of Microcystin-LR released into the water. In this paper, a floating photocatalyst for the photocatalytic inactivation of the harmful algae Microcystis aeruginosa (M. aeruginosa) was prepared using a simple sol-gel method, i.e., coating g-C₃N₄ coupled with Bi-doped TiO₂ on Al₂O₃-modified expanded perlite (CBTA for short). The impact of different molar ratios of Bi/Ti on CBTA was considered. The results indicated that Bi doping in TiO₂ inhibited photogenerated electron-hole pair recombination. With 6 h of visible light illumination, 75.9% of M. aeruginosa (initial concentration= 2.7 × 10⁶ cells/L) and 83.7% of Microcystin-LR (initial concentration= 100 μg/L) could be removed with the addition of 2 g/L CBTA-1% (i.e., Bi/Ti molar ratio= 1%). The key reactive oxygen species (ROSs) in the photocatalytic inactivation process are h⁺ and ^•OH. The induction of the Bi⁴⁺/Bi³⁺ species by the incorporation of Bi could narrow the bandgap of TiO₂, trap electrons, and enhance the stability of CBTA-1% in the solutions with coexisting environmental substances.     

Fate of microplastics in a coastal wastewater treatment plant: Microfibers could partially break through the integrated membrane system

• Fate of microplastics in integrated membrane system for water reuse was investigated. • Integrated membrane system has high removal efficiency (>98%) for microplastics. • Microplastics (>93%) were mainly removed through membrane bioreactor treatment. • Small scale fiber plastics (<200 μm) could break through reverse osmosis (RO) system. • The flux of microplastics maintained at 2.7 × 10¹¹ MPs/d after the RO treatment. Rare information on the fate of microplastics in the integrated membrane system (IMS) system in full-scale wastewater treatment plant was available. The fate of microplastics in IMS in a coastal reclaimed water plant was investigated. The removal rate of microplastics in the IMS system reached 93.2% after membrane bioreactor (MBR) treatment while that further increased to 98.0% after the reverse osmosis (RO) membrane process. The flux of microplastics in MBR effluent was reduced from 1.5 × 10¹³ MPs/d to 10.2 × 10¹¹ MPs/d while that of the RO treatment decreased to 2.7 × 10¹¹ MPs/d. Small scale fiber plastics (<200 μm) could break through RO system according to the size distribution analysis. The application of the IMS system in the reclaimed water plant could prevent most of the microplastics from being discharged in the coastal water. These findings suggested that the IMS system was more efficient than conventional activated sludge system (CAS) for the removal of microplastics, while the discharge of small scale fiber plastics through the IMS system should also not be neglected because small scale fiber plastics (<200 μm) could break through IMS system equipped with the RO system.     

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.     

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.     

An efficient resin for solid-phase extraction and determination by UPLCMS/MS of 44 pharmaceutical personal care products in environmental waters

• A hydrophilic resin (GCHM) was facile synthesis and characterized. • Average absolute recovery of GCHM (75.6%) performs better than Oasis^® HLB. • Detection limits of method (SPE-UPLC-MS/MS) ranged between 0.03 and 0.6 ng/L. • 22 PPCPs were determined in environmental waters ranging from 0.5 to 1590 ng/L. In this study, a hydrophilic resin named GCHM was fabricated based on poly(N-vinyl pyrrolidone-co-divinylbenzene), characterized, and applied as a solid-phase extraction (SPE) material. Up to 44 pharmaceuticals and personal care products (PPCPs) belonging to 10 classes were recovered in environmental water samples. Different variables affecting extraction, such as adsorbent amount, sample pH, and loading speed, were optimized. Under optimal conditions, the average absolute recovery of 44 PPCPs was 75.6% using GCHM, indicating a better performance than the commercial Oasis^® HLB. SPE with home-made hydrophilic polymeric sorbent followed by ultra-performance liquid chromatography and tandem mass spectrometry was validated, and the method achieved good linearity (r²>0.991, for all analytes). In addition, the method detection limits of target compounds ranged from 0.03 to 0.6 ng/L. The developed method was applied to determine PPCPs in 10 environmental water samples taken from the Yangtze River, Huaihe River, and Taihu Lake, 1 groundwater sample from Changzhou in Jiangsu Province, 1 wastewater sample from Xiamen and 2 seawater samples from the Jiulong River in Fujian Province, China. In these samples, 22 compounds were determined at levels ranging from 0.5 to 1590 ng/L.     

Light-induced variation in environmentally persistent free radicals and the generation of reactive radical species in humic substances

• Light irradiation increased the concentration of free radicals on HS. • The increased spin densities on HS readily returned back to the original value. • The “unstable” free radicals induced the formation of reactive radical species. • Reactive radicals’ concentration correlated strongly with EPFRs’ concentration. Environmentally persistent free radicals (EPFRs) in humic substances play an essential role in soil geochemical processes. Light is known to induce EPFRs formation for dissolved organic matter in aquatic environments; however, the impacts of light irradiation on the variation of EPFRs in soil humic substances remain unclear. In this study, humic acid, fulvic acid, and humin were extracted from peat soil and then in situ irradiated using simulated sunlight. Electron paramagnetic resonance spectroscopy results showed that with the increasing irradiation time, the spin densities and g-factors of humic substances rapidly increased during the initial 20 min and then gradually reached a plateau. After irradiation for 2h, the maximum spin density levels were up to 1.63 × 10¹⁷, 2.06 × 10¹⁷, and 1.77 × 10¹⁷ spins/g for the humic acid, fulvic acid, and humin, respectively. And the superoxide radicals increased to 1.05 × 10¹⁴–1.46 × 10¹⁴ spins/g while the alkyl radicals increased to 0.47 × 10¹⁴–1.76 × 10¹⁴ spins/g. The light-induced EPFRs were relatively unstable and readily returned back to their original state under dark and oxic conditions. Significant positive correlations were observed between the concentrations of EPFRs and reactive radical species (R² = 0.65–0.98, p<0.05), which suggested that the newly produced EPFRs contributed to the formation of reactive radical species. Our findings indicate that under the irradiation humic substances are likely to be more toxic and reactive in soil due to the formation of EPFRs.     

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.     

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.     

Enhanced catalytic oxidation of 2,4-dichlorophenol via singlet oxygen dominated peroxymonosulfate activation on CoOOH@Bi2O3 composite

• Bi₂O₃ cannot directly activate PMS. • Bi₂O₃ loading increased the specific surface area and conductivity of CoOOH. • Larger specific surface area provided more active sites for PMS activation. • Faster electron transfer rate promoted the generation of reactive oxygen species. • ¹O₂ was identified as dominant ROS in the CoOOH@Bi₂O₃/PMS system. Cobalt oxyhydroxide (CoOOH) has been turned out to be a high-efficiency catalyst for peroxymonosulfate (PMS) activation. In this study, CoOOH was loaded on bismuth oxide (Bi₂O₃) using a facile chemical precipitation process to improve its catalytic activity and stability. The result showed that the catalytic performance on the 2,4-dichlorophenol (2,4-DCP) degradation was significantly enhanced with only 11 wt% Bi₂O₃ loading. The degradation rate in the CoOOH@Bi₂O₃/PMS system (0.2011 min⁻¹) was nearly 6.0 times higher than that in the CoOOH/PMS system (0.0337 min⁻¹). Furthermore, CoOOH@Bi₂O₃ displayed better stability with less Co ions leaching (16.4% lower than CoOOH) in the PMS system. These phenomena were attributed to the Bi₂O₃ loading which significantly increased the conductivity and specific surface area of the CoOOH@Bi₂O₃ composite. Faster electron transfer facilitated the redox reaction of Co (III) / Co (II) and thus was more favorable for reactive oxygen species (ROS) generation. Meanwhile, larger specific surface area furnished more active sites for PMS activation. More importantly, there were both non-radical (¹O₂) and radicals (SO₄⁻•, O₂⁻•, and OH•) in the CoOOH@Bi₂O₃/PMS system and ¹O₂ was the dominant one. In general, this study provided a simple and practical strategy to enhance the catalytic activity and stability of cobalt oxyhydroxide in the PMS system.     

Significant increase of assimilable organic carbon (AOC) levels in MBR effluents followed by coagulation,ozonation and combined treatments: Implications for biostability control of reclaimed water

• Annual AOCs in MBR effluents were stable with small increase in warmer seasons. • Significant increase in AOC levels of tertiary effluents were observed. • Coagulation in prior to ozonation can reduce AOC formation in tertiary treatment. • ∆UV₂₅₄ and SUVA can be surrogates to predict the AOC changes during ozonation. As water reuse development has increased, biological stability issues associated with reclaimed water have gained attention. This study evaluated assimilable organic carbon (AOC) in effluents from a full-scale membrane biological reactor (MBR) plant and found that they were generally stable over one year (125–216 µg/L), with slight increases in warmer seasons. After additional tertiary treatments, the largest increases in absolute and specific AOCs were detected during ozonation, followed by coagulation-ozonation and coagulation. Moreover, UV₂₅₄ absorbance is known to be an effective surrogate to predict the AOC changes during ozonation. Applying coagulation prior to ozonation of MBR effluents for removal of large molecules was found to reduce the AOC formation compared with ozonation treatment alone. Finally, the results revealed that attention should be paid to seasonal variations in influent and organic fraction changes during treatment to enable sustainable water reuse.     

A novel strategy for gas mitigation during swine manure odour treatment using seaweed and a microbial consortium

• Comprehensive mitigation of gas emissions from swine manure was investigated. • Additives addition for mitigation of gas from the manure has been developed. • Sargassum horneri, seaweed masking strategy controlled gas by 90%-100%. • Immediate reduction in emitted gas and improving air quality has been determined. • Microbial consortium with seaweed completely controlled gas emissions by 100%. Gas emissions from swine farms have an impact on air quality in the Republic of Korea. Swine manure stored in deep pits for a long time is a major source of harmful gas emissions. Therefore, we evaluated the mitigation of emissions of ammonia (NH₃), hydrogen sulfide (H₂S) and amine gases from swine manure with biological products such as seaweed (Sargassum horneri) and a microbial consortium (Bacillus subtilis (1.2 × 10⁹ CFU/mL), Thiobacillus sp. (1.0 × 10¹⁰ CFU/mL) and Saccharomyces cerevisiae (2.0 × 10⁹ CFU/mL)) used as additives due to their promising benefits for nutrient cycling. Overall, seaweed powder masking over two days provided notable control of over 98%-100% of the gas emissions. Furthermore, significant control of gas emissions was especially pronounced when seaweed powder masking along with a microbial consortium was applied, resulting in a gas reduction rate of 100% for NH₃, amines and H₂S over 10 days of treatment. The results also suggested that seaweed powder masking and a microbial consortium used in combination to reduce the gas emissions from swine manure reduced odour compared with that observed when the two additives were used alone. Without the consortium, seaweed decreased total volatile fatty acid (VFA) production. The proposed novel method of masking with a microbial consortium is promising for mitigating hazardous gases, simple, and environmentally beneficial. More research is warranted to determine the mechanisms underlying the seaweed and substrate interactions.     

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.     

The treatment of black-odorous water using tower bipolar electro-flocculation including the removal of phosphorus,turbidity, sulfion,and oxygen enrichment

• An innovative bubble column tower BPE was designed to treat the black-odorous water. • PO₄³⁻, S²⁻ and turbidity were removed, and dissolved oxygen was enriched in the BPE. • An aluminum bipolar electrode gave the best oxygen enrichment and pollutant removal. • Changes of microorganisms confirmed the improvement in water quality achieved. The large amount of municipal wastewater discharged into urban rivers sometimes exceeds the rivers’ self-purification capacity leading to black-odorous polluted water. Electro-flocculation has emerged as a powerful remediation technology. Electro-flocculation in a bubble column tower with a bipolar electrode (BPE) was tested in an attempt to overcome the high resistance and weak gas-floatation observed with a monopolar electrode (MPE) in treating such water. The BPE reactor tested had a Ti/Ta₂O₅-IrO₂ anode and a graphite cathode with an iron or aluminum bipolar electrode suspended between them. It was tested for its ability to reduce turbidity, phosphate and sulphion and to increase the concentration of dissolved oxygen. The inclusion of the bipolar electrode was found to distinctly improved the system’s conductivity. The system’s electro-flocculation and electrical floatation removed turbidity, phosphate and sulphion completely, and the dissolved oxygen level improved from 0.29 to 6.28 mg/L. An aluminum bipolar electrode performed better than an iron one. Changes in the structure of the microbial community confirmed a significant improvement in water quality.     

Sea salt bittern-driven forward osmosis for nutrient recovery from black water: A dual waste-to-resource innovation via the osmotic membrane process

• A dual “waste-to-resource” application of FO was proposed. • Performance of sea salt bittern as an economic FO draw solution was evaluated. • High quality struvite recovery from black water using FO was demonstrated. • Feed pH is a key factor to control the form of recovered phosphorous. A dual “waste-to-resource” innovation in nutrient enrichment and recovery from domestic black water using a sea salt bittern (SSB)-driven forward osmosis (FO) process is proposed and demonstrated. The performance of SSB as a “waste-to-resource” draw solution for FO was first evaluated. A synthetic SSB-driven FO provided a water flux of 25.67±3.36 L/m²⋅h, which was 1.5‒1.7 times compared with synthetic seawater, 1 M NaCl, and 1 M MgCl₂. Slightly compromised performance regarding reverse solute selectivity was observed. In compensation, the enhanced reverse diffusion of Mg²⁺ suggested superior potential in terms of recovering nutrients in the form of struvite precipitation. The nutrient enrichment was performed using both the pre-filtered influent and effluent of a domestic septic tank. Over 80% of phosphate-P recovery was achieved from both low- and high-strength black water at a feed volume reduction up to 80%‒90%. With an elevated feed pH (~9), approximately 60%‒85% enriched phosphate-P was able to be recovered in the form of precipitated stuvite. Whereas the enrichment performance of total Kjeldahl nitrogen (TKN) largely differed depending on the strength of black water. Improved concentration factor (i.e., 3-folds) and retention (>60%) of TKN was obtained in the high-nutrient-strength black water at a feed volume reduction of 80%, in comparison with a weak TKN enrichment observed in low-strength black water. The results suggested a good potential for nutrient recovery based on this dual “waste-to-resource” FO system with proper management of membrane cleaning.     

Redox reactions of iron and manganese oxides in complex systems

• Mechanisms of redox reactions of Fe- and Mn-oxides were discussed. • Oxidative reactions of Mn- and Fe-oxides in complex systems were reviewed. • Reductive reaction of Fe(II)/iron oxides in complex systems was examined. • Future research on examining the redox reactivity in complex systems was suggested. Conspectus Redox reactions of Fe- and Mn-oxides play important roles in the fate and transformation of many contaminants in natural environments. Due to experimental and analytical challenges associated with complex environments, there has been a limited understanding of the reaction kinetics and mechanisms in actual environmental systems, and most of the studies so far have only focused on simple model systems. To bridge the gap between simple model systems and complex environmental systems, it is necessary to increase the complexity of model systems and examine both the involved interaction mechanisms and how the interactions affected contaminant transformation. In this Account, we primarily focused on (1) the oxidative reactivity of Mn- and Fe-oxides and (2) the reductive reactivity of Fe(II)/iron oxides in complex model systems toward contaminant degradation. The effects of common metal ions such as Mn²⁺ , Ca²⁺, Ni²⁺, Cr³⁺ and Cu²⁺, ligands such as small anionic ligands and natural organic matter (NOM), and second metal oxides such as Al, Si and Ti oxides on the redox reactivity of the systems are briefly summarized.