Effectiveness of tertiary treatment processes in removing different classes of emerging contaminants from domestic wastewater

● Different advanced treatment processes were tested for ECs removal from wastewater. ● UV radiation showed low to moderate removal for 5 of the 38 micropollutants. ● Among tested membrane processes, nanofiltration showed the better performance. ● The use of PAC achieved high or partially removal for 31 out of the 38 compounds. ● The environmental and economical evaluation of a pilot-scale PAC unit is suggested. In this work, 38 different organic emerging contaminants (ECs), belonging to various chemical classes such as pharmaceuticals (PhCs), endocrine-disrupting chemicals (EDCs), benzotriazoles (BTRs), benzothiazoles (BTHs), and perfluorinated compounds (PFCs), were initially identified and quantified in the biologically treated wastewater collected from Athens’ (Greece) Sewage Treatment Plant (STP). Processes already used in existing STPs such as microfiltration (MF), nanofiltration (NF), ultrafiltration (UF), UV radiation, and powdered activated carbon (PAC) were assessed for ECs’ removal, under the conditions that represent their actual application for disinfection or advanced wastewater treatment. The results indicated that MF removed only one out of the 38 ECs and hence it was selected as pretreatment step for the other processes. UV radiation in the studied conditions showed low to moderate removal for 5 out of the 38 ECs. NF showed better results than UF due to the smaller pore sizes of the filtration system. However, this enhancement was observed mainly for 8 compounds originating from the classes of PhCs and PFCs, while the removal of EDCs was not statistically significant. Among the various studied technologies, PAC stands out due to its capability to sufficiently remove most ECs. In particular, removal rates higher than 70% were observed for 9 compounds, 22 were partially removed, while 7 demonstrated low removal rates. Based on our screening experiments, future research should focus on scaling-up PAC in actual conditions, combining PAC with other processes, and conduct a complete economic and environmental assessment of the treatment.     

Photo-induced surface frustrated Lewis pairs for promoted photocatalytic decomposition of perfluorooctanoic acid

● Terminal carboxylate group activation is PFOA degradation’s rate-limiting step. ● Bi₃O(OH)(PO₄)₂ with surface frustrated Lewis pairs (SFLPs) efficiently degrade PFOA. ● Photo-induced Lewis acidic sites and proximal surface hydroxyls constitute SFLPs. ● SFLPs act as collection centers to effectively adsorb PFOA. ● SFLPs endow accessible pathways for photogenerated holes rapid transfer to PFOA. Heterogeneous photocatalysis has gained substantial research interest in treating per- and polyfluoroalkyl substances (PFAS)-contaminated water. However, sluggish degradation kinetics and low defluorination efficiency compromise their practical applications. Here, we report a superior photocatalyst, defected Bi₃O(OH)(PO₄)₂, which could effectively degrade typical PFAS, perfluorooctanoic acid (PFOA), with high defluorination efficiency. The UV light irradiation could in situ generate oxygen vacancies on Bi₃O(OH)(PO₄)₂ through oxidation of the lattice hydroxyls, which further promotes the formation of Lewis acidic coordinately unsaturated bismuth sites. Then, the Lewis acidic sites couple with the proximal surface hydroxyls to constitute the surface frustrated Lewis pairs (SFLPs). With the in-depth spectroscopic analysis, we revealed that the photo-induced SFLPs act as collection centers to effectively adsorb PFOA and endow accessible pathways to transfer photogenerated holes to PFOA rapidly. Consequently, activation of the terminal carboxyl, a rate-limiting step for PFOA decomposition, could be easily achieved over the defected Bi₃O(OH)(PO₄)₂ photocatalyst. These results suggest that SFLPs exhibit great potential in developing highly efficient photocatalysts to degrade persistent organic pollutants.     

Insights into the electron transfer mechanisms of permanganate activation by carbon nanotube membrane for enhanced micropollutants degradation

● A CNT filter enabled effective KMnO₄ activation via facilitated electron transfer. ● Ultra-fast degradation of micropollutants were achieved in KMnO₄/CNT system. ● CNT mediated electron transfer process from electron-rich molecules to KMnO₄. ● Electron transfer dominated organic degradation. Numerous reagents have been proposed as electron sacrificers to induce the decomposition of permanganate (KMnO₄) by producing highly reactive Mn species for micropollutants degradation. However, this strategy can lead to low KMnO₄ utilization efficiency due to limitations associated with poor mass transport and high energy consumption. In the present study, we rationally designed a catalytic carbon nanotube (CNT) membrane for KMnO₄ activation toward enhanced degradation of micropollutants. The proposed flow-through system outperformed conventional batch reactor owing to the improved mass transfer via convection. Under optimal conditionals, a > 70% removal (equivalent to an oxidation flux of 2.43 mmol/(h·m²)) of 80 μmol/L sulfamethoxazole (SMX) solution can be achieved at single-pass mode. The experimental analysis and DFT studies verified that CNT could mediate direct electron transfer from organic molecules to KMnO₄, resulting in a high utilization efficiency of KMnO₄. Furthermore, the KMnO₄/CNT system had outstanding reusability and CNT could maintain a long-lasting reactivity, which served as a green strategy for the remediation of micropollutants in a sustainable manner. This study provides new insights into the electron transfer mechanisms and unveils the advantages of effective KMnO₄ utilization in the KMnO₄/CNT system for environmental remediation.     

Numerical modeling and performance evaluation of passive convergence-permeable reactive barrier (PC-PRB)

● A 2D finite-element solute transport model, PRB-Trans, is developed. ● PC-PRB can significantly improve the remediation efficiency of PRB. ● PC-PRB can considerably reduce the required PRB dimensions and materials costs. ● The required PRB length decreases with the increase of pipe length, L _p. The passive convergence-permeable reactive barrier (PC-PRB) was proposed to address the limitations of traditional PRB configurations. To evaluate the hydraulic and pollutant removal performance of the PC-PRB system, we developed a simulation code named PRB-Trans. This code uses the two-dimensional (2D) finite element method to simulate groundwater flow and solute transport. Case studies demonstrate that PC-PRB technology is more efficient and cost-effective than continuous permeable reactive barrier (C-PRB) in treating the same contaminated plume. Implementation of PC-PRB technology results in a 33.3% and 72.7% reduction in PRB length (L_PRB) and height (H_PRB), respectively, while increasing 2D horizontal and 2D vertical pollutant treatment efficiencies of PRB by 87.8% and 266.8%, respectively. In addition, the PC-PRB technology has the ability to homogenize the pollutant concentration and pollutant flux through the PRB system, which can mitigate the problems arising from uneven distribution of pollutants in the C-PRB to some extent. The L_PRB required for PC-PRB decreases as the water pipe length (L_p) increases, while the H_PRB required initially decreases and then increases with increasing L_p. The effect of passive well height (H_w) on H_PRB is not as significant as that of L_p on H_PRB. Overall, PC-PRB presents a promising and advantageous PRB configuration in the effective treatment of various types of contaminated plumes.     

Revealing the GHG reduction potential of emerging biomass-based CO2 utilization with an iron cycle system

● Greenhouse gas mitigation by biomass-based CO₂ utilization with a Fe cycle system. ● The system including hydrothermal CO₂ reduction with Fe and Fe recovery by biomass. ● The reduction potential quantified by experiments, simulations, and an ex-ante LCA. ● The greatest GHG reduction potential is −34.03 kg CO₂-eq/kg absorbed CO₂. ● Ex-ante LCA supports process optimization to maximize GHG reduction potential. CO₂ utilization becomes a promising solution for reducing anthropogenic greenhouse gas (GHG) emissions. Biomass-based CO₂ utilization (BCU) even has the potential to generate negative emissions, but the corresponding quantitative evaluation is limited. Herein, the biomass-based CO₂ utilization with an iron cycle (BCU-Fe) system, which converts CO₂ into formate by Fe under hydrothermal conditions and recovers Fe with biomass-derived glycerin, was investigated. The GHG reduction potential under various process designs was quantified by a multidisciplinary method, including experiments, simulations, and an ex-ante life-cycle assessment. The results reveal that the BCU-Fe system could bring considerable GHG emission reduction. Significantly, the lowest value is −34.03 kg CO₂-eq/kg absorbed CO₂ (−2.44 kg CO₂-eq/kg circulated Fe) with the optimal yield of formate (66%) and Fe (80%). The proposed ex-ante evaluation approach not only reveals the benefits of mitigating climate change by applying the BCU-Fe system, but also serves as a generic tool to guide the industrialization of emerging carbon-neutral technologies.     

Microplastics in municipal wastewater treatment plants: a case study of Denizli/Turkey

● High amounts of microplastics are released to receiving media from WWTPs. ● The effect of classical treatment processes on MP removal is important. ● MP load in the effluent of WWTPs is important for developing treatment technology. ● Additional physical treatment could help further reduce MP discharge. Plastic particles smaller than 5 mm are microplastics. They are among the significant pollutants that recently attracted attention. Great quantities of microplastics enter the sewage system daily and reach wastewater treatment plants (WWTPs). As a result, WWTPs are potential microplastic sources. Hence, they create a pathway for microplastics to reach aquatic environments with treated wastewater discharge. Studies on microplastic characterization in WWTPs have gained momentum in academia. This study investigates the abundance, size, shape, color, polymer type, and removal efficiencies of microplastics in a municipal wastewater treatment plant (WWTP) in Denizli/Turkey. The results showed that the dominant microplastic shape in wastewater samples was fibers (41.78%–60.77%) in the 100–500 µm (58.57%–80.07%) size range. Most of the microplastics were transparent-white (32.86%–58.93%). The dominant polymer types were polyethylene (54.05%) and polyethylene vinyl acetate (37.84%) in raw wastewater. Furthermore, the microplastic removal efficiencies of the Denizli Central WWTP as a whole and for individual treatment units were evaluated. Although the microplastic pollution removal efficiency of the Denizli Central WWTP was over 95%, the microplastic concentration discharged daily into the receiving environment was considerably high (1.28 × 10¹⁰ MP/d). Thus, Denizli Central WWTP effluents result in a high volume of emissions in terms of microplastic pollution with a significant daily discharge to the Çürüksu Stream.     

Electrocatalytic reduction of nitrate using Pd-Cu modified carbon nanotube membranes

● Pd-Cu modified CNT membranes were prepared successfully by electrodeposition method. ● The deposition voltage and deposition time were optimized for Pd-Cu co-deposition. ● NO₃⁻-N was removed efficiently from water by Pd-Cu modified CNT membranes. ● The presence of dissolved oxygen did not affect the nitrate reduction performance. ● Mass transfer rate was promoted significantly with the increase in membrane flux. Excessive nitrate in water is harmful to the ecological environment and human health. Electrocatalytic reduction is a promising technology for nitrate removal. Herein, a Pd-Cu modified carbon nanotube membrane was fabricated with an electrodeposition method and used to reduce nitrate in a flow-through electrochemical reactor. The optimal potential and duration for codeposition of Pd and Cu were −0.7 V and 5 min, respectively, according to linear scan voltammetry results. The membrane obtained with a Pd:Cu ratio of 1:1 exhibited a relatively high nitrate removal efficiency and N₂ selectivity. Nitrate was almost completely reduced (~99 %) by the membrane at potentials lower than −1.2 V. However, −0.8 V was the optimal potential for nitrate reduction in terms of both nitrate removal efficiency and product selectivity. The nitrate removal efficiency was 56.2 %, and the N₂ selectivity was 23.8 % for the Pd:Cu=1:1 membrane operated at −0.8 V. Nitrate removal was enhanced under acidic conditions, while N₂ selectivity was decreased. The concentrations of Cl⁻ ions and dissolved oxygen showed little effect on nitrate reduction. The mass transfer rate constant was greatly improved by 6.6 times from 1.14 × 10⁻³ m/h at a membrane flux of 1 L/(m²·h) to 8.71 × 10⁻³ m/h at a membrane flux of 15 L/(m²·h), which resulted in a significant increase in the nitrate removal rate from 13.6 to 133.5 mg/(m²·h). These findings show that the Pd-Cu modified CNT membrane is an efficient material for nitrate reduction.     

Removal of virus aerosols by the combination of filtration and UV-C irradiation

● The removal of virus aerosols by filtration and UV-C irradiation was proposed. ● The filtration efficiency for virus aerosols was affected by the filtration rate. ● The inactivation rate by UV-C was not linear with irradiation intensity or time. ● The virus trapped by filter material had a shielding effect on UV-C irradiation. The COVID-19 pandemic remains ever prevalent and afflicting—partially because one of its transmission pathways is aerosol. With the widely used central air conditioning systems worldwide, indoor virus aerosols can rapidly migrate, thus resulting in rapid infection transmission. It is therefore important to install microbial aerosol treatment units in the air conditioning systems, and we herein investigated the possibility of combining such filtration with UV irradiation to address virus aerosols. Results showed that the removal efficiency of filtration towards f2 and MS2 phages depended on the type of commercial filter material and the filtration speed, with an optimal velocity of 5 cm/s for virus removal. Additionally, it was found that UV irradiation had a significant effect on inactivating viruses enriched on the surfaces of filter materials; MS2 phages had greater resistance to UV-C irradiation than f2 phages. The optimal inactivation time for UV-C irradiation was 30 min, with higher irradiation times presenting no substantial increase in inactivation rate. Moreover, excessive virus enrichment on the filters decreased the inactivation effect. Timely inactivation is therefore recommended. In general, the combined system involving filtration with UV-C irradiation demonstrated a significant removal effect on virus aerosols. Moreover, the system is simple and economical, making it convenient for widespread implementation in air-conditioning systems.     

Tailoring the simultaneous abatement of methanol and NOx on Sb-Ce-Zr catalysts via copper modification

● Cu addition enhances CH₃OH oxidation and alleviates its inhibitory effect on SCR. ● Cu addition improves the activation of SCR reactants in the presence of methanol. ● Damaged structure by more Cu addition decreases specific surface area and acidity. ● Excessive Cu addition would lead to the narrowing of SCR temperature window. Simultaneously removal of NO_x and VOCs over NH₃-SCR catalysts have attracted lots of attention recently. However, the presence of VOCs would have negative effect on deNO_x efficiency especially at low temperature. In this study, copper modification onto Sb_0.5CeZr₂O_x (SCZ) catalyst were performed to enhance the catalytic performance for simultaneous control of NO_x and methanol. It was obtained that copper addition could improve the low-temperature activity of both NO_x conversion and methanol oxidation, where the optimal catalyst (Cu_0.05SCZ) exhibited a deNO_x activity of 96% and a mineralization rate of 97% at 250 °C, which are around 10% higher than that of Cu free sample. The characterization results showed that copper addition could obviously enhance the redox capacity of the catalysts. As such, the inhibition effect of methanol incomplete oxidation on NO adsorption and NH₃ activation were then lessened and the conversion of surface formamide species were also accelerated, resulting in the rising of NO_x conversion at low temperature. However, excessive copper addition would damage the Sb-Ce-Zr oxides solid solution structure owing to Cu-Ce strong interactions, decreasing the surface area and acidity. Meanwhile, due to easier over-oxidation of NH₃ with more Cu addition, the temperature window for NO_x conversion would become quite narrow. These findings could provide useful guidelines for the synergistic removal of VOCs over SCR catalyst in real application.     

Enhancement of extracellular Cr(VI) reduction for anammox recovery using hydrazine: performance,pathways, and mechanism

● N₂H₄ addition enhanced and recovered anammox performance under Cr(VI) stress. ● N₂H₄ accelerated electron transfer of Cr(VI) reduction for detoxification. ● N₂H₄ enhanced anammox metabolism for activity recovery from Cr(VI) inhibition. ● Extracellular Cr(VI) reduction to less toxic Cr(III) was the dominant mechanism. The hexavalent chromium (Cr(VI)) would frequently impose inhibition to anaerobic ammonium oxidation (anammox) process, hindering the efficiency of nitrogen removal in wastewater treatment. Hydrazine (N₂H₄), which is an intermediate product of anammox, participates in intracellular metabolism and extracellular Cr(VI) reduction. However, the roles of N₂H₄-induced intracellular metabolism and extracellular reduction in nitrogen removal under Cr(VI) stress remain unclear. The addition of 3.67 mg/L of N₂H₄ increased the anammox activity by 17%. As an intermediate, N₂H₄ enhanced anammox metabolism by increasing the heme c content and electron transfer system activity. As a reductant, N₂H₄ accelerated the reduction of c-Cyts-mediated extracellular Cr(VI) to the less toxic Cr(III). Extracellular Cr(III) accounts for 74% of the total Cr in a Cr(VI)-stressed anammox consortia. These findings highlight that N₂H₄-induced extracellular Cr(VI) reduction is the dominant mechanism for the survival of anammox consortia. We also found that N₂H₄ increased the production of extracellular polymeric substances to sequester excessive Cr(VI) and produced Cr(III). Taken together, the study findings suggest a potential strategy for enhancing nitrogen removal from ammonium-rich wastewater contaminated with Cr(VI).     

Impacts of backwashing on micropollutant removal and associated microbial assembly processes in sand filters

● Backwashing in sand filters with 2-h and 4-h EBCTs was simulated. ● Removal efficiency of five micropollutants recovered within 2 d at 2-h EBCT. ● Active biomass of sand filters recovered within 2 d under two EBCTs. ● Microbial composition gradually recovered to pre-backwashing level at 2-h EBCT. ● Recovered microbes only accounted for 15.55 %–25.69 % in the sand filters at 4-h EBCT. Backwashing is crucial for preventing clogging of sand filters. However, few studies have investigated the effect of backwashing on micropollutant removal and the dynamic changes in the microbial community in sand filters. Here, we used a series of manganese and quartz sand filters under empty bed contact times (EBCTs) of 2 h and 4 h to explore variations in micropollutant degradation and temporal dynamics of the microbial community after backwashing. The results showed that the removal efficiencies of caffeine, sulfamethoxazole, sulfadiazine, trimethoprim, atrazine, and active biomass recovered within 2 d after backwashing in both types of sand filters at 2-h EBCT, but the recovery of sulfadiazine and trimethoprim was not observed at 4-h EBCT. Moreover, the removal efficiency of atenolol increased after backwashing in the manganese sand filters, whereas maintained almost complete removal efficiency in the quartz sand filters at both EBCTs. Pearson correlation analysis indicated that microbial community composition gradually recovered to the pre-backwashing level (R increased from 0.53 to 0.97) at 2-h EBCT, but shifted at 4-h EBCT (R < 0.25) after backwashing. Furthermore, the compositions of the recovered, depleted, and improved groups of microbes were distinguished by applying hierarchical clustering to the differentially abundant amplicon sequence variants. The cumulative relative abundance of recovered microbes at 2-h EBCT was 82.76 % ± 0.43 % and 46.82 % ± 4.34 % in the manganese and quartz sand filters, respectively. In contrast, at 4-h EBCT, the recovered microbes dropped to 15.55 %–25.69 % in both types of sand filters.     

Highly effective visible-photocatalytic hydrogen evolution and simultaneous organic pollutant degradation over an urchin-like oxygen-doped MoS2/ZnIn2S4 composite

● An urchin-like OMS/ZIS composite was fabricated by a facile solvothermal method. ● The OMS/ZIS exhibits superior photocatalytic H₂ evolution for organics degradation. ● A probable mechanism of dual-functional photocatalysis was proposed in detail. ● This work provides an inspiration for rational design of dual-functional catalysts. Achieving hydrogen production and simultaneous decomposition of organic pollutants through dual-functional photocatalytic reactions has received increasing attention due to the environmentally friendly and cost-effective characteristics of this approach. In this work, an urchin-like oxygen-doped MoS₂/ZnIn₂S₄ (OMS/ZIS) composite was fabricated for the first time using a simple solvothermal method. The unique microstructure with abundant active sites and fast charge transfer channels further shortened the charge migration distance and compressed carrier recombination. The obtained composite exhibited an efficient H₂ evolution reaction rate of 12.8 mmol/g/h under visible light, which was nearly times higher than pristine ZnIn₂S₄, and the apparent quantum efficiency was 14.9% (420 nm). The results of the simultaneous photocatalytic H₂ evolution and organic pollutant decomposition test were satisfactory, resulting in decomposition efficiencies of resorcinol, tetracycline, and bisphenol A that reached 41.5%, 63.5%, and 53.0% after 4 h, respectively, and the highest H₂ evolution rate was 672.7 μmol/g/h for bisphenol A. Furthermore, natural organic matter (NOM) abundantly found in actual water was adopted as an electron donor for H production under simulated sunlight irradiation, indicating the promising practicability of simultaneous hydrogen evolution and NOM decomposition. Moreover, the mechanisms of the dual-purpose photocatalytic reactions, as well as the synergistic effect between the molecular structures of the organic pollutants and the corresponding adsorption behavior on the photocatalyst surface were illustrated in detail. These obtained results may serve as an inspiration for the rational design of highly efficient, dual-functional photocatalysts in the future.     

Stress response to nanoplastics with different charges in Brassica napus L. during seed germination and seedling growth stages

● Higher concentrations of PS, PS-NH₂ and PS-SO₃H inhibited seed germination. ● PS, PS-NH₂ and PS-SO₃H influenced seedling growth in a dose-dependent manner. ● PS, PS-NH₂ and PS-SO₃H reduced essential nutrients uptake and plant quality. ● PS, PS-NH₂ and PS-SO₃H increased antioxidant enzyme activities and MDA content. ● Nanoplastic toxicity was related to surface charges. Nanoplastic pollution has become a significant problem in farmland systems worldwide. However, research on the effects of nanoplastics (NPs) with different charges on field crops is still limited. In our study, NPs with different charges, including unmodified polystyrene nanoplastics (PS), positively charged polystyrene nanoplastics (PS-NH₂), and negatively charged polystyrene nanoplastics (PS-SO₃H), were investigated for their impacts on seed germination and seedling growth of rape. The results showed that seed water uptake (after 12 h), seed germination, seed vigour, and relative root elongation were all significantly reduced under exposure to NPs (200 mg/L). Similarly, remarkable decreases in plant biomass (root weight, shoot weight), growth (root length, plant height), photosynthesis ability (chlorophyll a, chlorophyll b, carotenoids), essential nutrient uptake (Fe, Mn, Zn, Cu), and plant quality (soluble protein, soluble sugar, crude fibre content) of rape seedlings were also observed after exposure to NPs. Among the three kinds of NPs, PS-NH₂ showed stronger effects. Moreover, superoxide dismutase, peroxidase, and catalase activities of rape seedlings were changed, and the content of malondialdehyde was significantly increased under exposure to NPs. Furthermore, positively charged PS-NH₂ showed stronger effects on the phenotype, physiology, biochemistry, nutrient uptake, and plant quality of rape. Notably, a comprehensive toxicity evaluation revealed that PS-NH₂ had the strongest toxicity to rape. The present study provides important implications for the interaction and risk assessment of NPs and crops in soil-plant systems.     

Long-term exposure to air pollution and cerebrovascular disease: findings from Beijing Health Management Cohort study

● This study explored the long-term association by double robust additive models. ● Individual exposure concentrations were assessed by integrating GAM, LUR and BPNN. ● PM_2.5, SO₂ and NO₂ are positively associated with cerebrovascular disease. ● CO could reduce the risk of cerebrovascular disease with the highest robustness. ● The elderly, women and people with normal BMI are at higher risk for air pollution. The relationship between air pollution and cerebrovascular disease has become a popular topic, yet research findings are highly heterogeneous. This study aims to investigate this association based on detailed individual health data and a precise evaluation of their exposure levels. The integrated models of generalized additive model, land use regression model and back propagation neural network were used to evaluate the exposure concentrations. And doubly robust additive model was conducted to explore the association between cerebrovascular disease and air pollution after adjusted for demographic characteristics, physical examination, disease information, geographic and socioeconomic status. A total of 25097 subjects were included in the Beijing Health Management Cohort from 2013 to 2018. With a 1 μg/m³ increase in the concentrations of PM_2.5, SO₂ and NO₂, the incidence risk of cerebrovascular disease increased by 1.02 (95% CI: 1.008–1.034), 1.06 (95% CI: 1.034–1.095) and 1.02 (95% CI: 1.010–1.029) respectively. Whereas CO exposure could decrease the risk, with an odds ratio of 0.38 (95% CI: 0.212–0.626). In the subgroup analysis, individuals under the age of 50 with normal BMI were at higher risk caused by PM_2.5, and SO₂ was considered more hazardous to women. Meanwhile, the protective effect of CO on women and those with normal BMI was stronger. Successful reduction of long-term exposure to PM_2.5, SO₂ and NO₂ would lead to substantial benefits for decrease the risk of cerebrovascular disease especially for the health of the susceptible individuals.     

Non-toxic,high selectivity process for the extraction of precious metals from waste printed circuit boards

● Au, Ag and Pd were recovered from WPCBs with high efficiencies. ● Au leaching is strictly dependent on WPCB size and reagent concentration. ● High Ag extraction efficiencies are achieved regardless of the WPCB size. ● Pd leaching works better with small and medium WPCB sizes. ● The leaching results suggest the possibility of selective recovery of metals. The work presented here focused on the extraction of gold (Au), silver (Ag) and palladium (Pd) from electronic waste using a solution of ammonium thiosulfate. Thiosulfate was used as a valid alternative to cyanide for precious metal extractions, due to its non-toxicity and high selectivity. The interactions between sodium thiosulfate, total ammonia/ammonium, precious metal concentrations and the particle size of the waste printed circuit boards (WPCBs) were studied by the response surface methodology (RSM) and the principal component analysis (PCA) to maximize precious metal mobilization. Au extraction reached a high efficiency with a granulometry of less than 0.25 mm, but the consumption of reagents was high. On the other hand, Ag extraction depended neither on thiosulfate/ammonia concentration nor granulometry of WPCBs and it showed efficiency of 90% also with the biggest particle size (0.50 < Ø < 1.00 mm). Pd extraction, similarly to Au, showed the best efficiency with the smallest and the medium WPCB sizes, but required less reagents compared to Au. The results showed that precious metal leaching is a complex process (mainly for Au, which requires more severe conditions in order to achieve high extraction efficiencies) correlated with reagent concentrations, precious metal concentrations and WPCB particle sizes. These results have great potentiality, suggesting the possibility of a more selective recovery of precious metals based on the different granulometry of the WPCBs. Furthermore, the high extraction efficiencies obtained for all the metals bode well in the perspective of large-scale applications.     

Functional flax fiber with UV-induced switchable wettability for multipurpose oil-water separation

● A PAA-ZnO-HDTMS flax fiber with UV-induced switchable wettability was developed. ● The property of flax fiber could be switched from hydrophobicity to hydrophilicity. ● The mechanism of the acquired UV-induced switchable wettability was discussed. ● The developed flax fiber was successfully used for multipurpose oil-water separation. The large number of oily wastewater discharges and oil spills are bringing about severe threats to environment and human health. Corresponding to this challenge, a functional PAA-ZnO-HDTMS flax fiber with UV-induced switchable wettability was developed for efficient oil-water separation in this study. The developed flax fiber was obtained through PAA grafted polymerization and then ZnO-HDTMS nanocomposite immobilization. The as-prepared PAA-ZnO-HDTMS flax fiber was hydrophobic initially and could be switched to hydrophilic through UV irradiation. Its hydrophobicity could be easily recovered through being stored in dark environment for several days. To optimize the performance of the PAA-ZnO-HDTMS flax fiber, the effects of ZnO and HDTMS concentrations on its switchable wettability were investigated. The optimized PAA-ZnO-HDTMS flax fiber had a large water contact angle (~130°) in air and an extremely small oil contact angle (~0°) underwater initially. After UV treatment, the water contact angle was decreased to 30°, while the underwater oil contact angle was increased to more than 150°. Based on this UV-induced switchable wettability, the developed PAA-ZnO-HDTMS flax fiber was applied to remove oil from immiscible oil-water mixtures and oil-in-water emulsion with great reusability for multiple cycles. Thus, the developed flax fiber could be further fabricated into oil barrier or oil sorbent for oil-water separation, which could be an environmentally-friendly alternative in oil spill response and oily wastewater treatment.     

Efficient production of hydrogen peroxide in microbial reverse-electrodialysis cells coupled with thermolytic solutions

● Appreciable H₂O₂ production rate was achieved in MRCs utilizing NH₄HCO₃ solutions. ● Carbon black outperformed activated carbon as the catalyst for H₂O₂ production. ● The optimum carbon black loading for H₂O₂ production on air-cathode was 10 mg/cm². ● The optimum number of cell pairs was determined to be three. ● A maximum power density of 980 mW/m² was produced by MRCs with 5 cell pairs. H₂O₂ was produced at an appreciable rate in microbial reverse-electrodialysis cells (MRCs) coupled with thermolytic solutions, which can simultaneously capture waste heat as electrical energy. To determine the optimal cathode and membrane stack configurations for H₂O₂ production, different catalysts, catalyst loadings and numbers of membrane cell pairs were tested. Carbon black (CB) outperformed activated carbon (AC) for H₂O₂ production, although AC showed higher catalytic activity for oxygen reduction. The optimum CB loading was 10 mg/cm² in terms of both the H₂O₂ production rate and power production. The optimum number of cell pairs was determined to be three based on a tradeoff between H₂O₂ production and capital costs. A H₂O₂ production rate as high as 0.99 ± 0.10 mmol/(L·h) was achieved with 10 mg/cm² CB loading and 3 cell pairs, where the H₂O₂ recovery efficiency was 52 ± 2% and the maximum power density was 780 ± 37 mW/m². Increasing the number of cell pairs to five resulted in an increase in maximum power density (980 ± 21 mW/m²) but showed limited effects on H₂O₂ production. These results indicated that MRCs can be an efficient method for sustainable H₂O₂ production.     

Evaluation of activated sludge properties’ changes in industrial-wastewater pre-treatment: role of residual aluminum hydrolyzed species with different polymerization degree

● Medium poly Al salts dominated the PAC residual salts with a rational dosage. ● Settlement flocculation effect under medium poly Al salts showed a better trend. ● Complex of medium poly Al salts and enzymes promoted cell activity. ● Medium poly Al salts were beneficial to the effluent indexes. With the widespread introduction of pre-coagulation prior to the biological unit in various industrial wastewater treatments, it is noteworthy that long-term accumulation of residual coagulants has certains effect on both micro and macro characteristics of activated sludge (AS). In this study, the morphology distributions of residual aluminum salts (RAS) and their effects on the removal efficiency of AS were investigated under different PAC concentrations. The results showed that the dominance of medium polymeric RAS, formed under an appropriate PAC dose of 20 mg/L enhanced the hydrophobicity, flocculation, and sedimentation performances of AS, as well as the enzymatic activity in cells in the sludge system, improving the main pollutants removal efficiency of the treatment system. Comparatively the species composition with monomer and dimer / high polymer RAS as the overwhelming parts under an over-dosed PAC concentration of 55 mg/L resulted in excessive secretion of EPS with loose flocs structure and conspicuous inhibition of cellular activity, leading to the deterioration of physico-chemical and biological properties of AS. Based on these findings, this study can shed light on the role of the RAS hydrolyzed species distributions, closely relevant to Al dosage, in affecting the comprehensive properties of AS and provide a theoretical reference for coagulants dosage precise control in the pretreatment of industrial wastewater.     

Distribution,enrichment mechanism and risk assessment for fluoride in groundwater: a case study of Mihe-Weihe River Basin,China

● High fluorine is mainly HCO₃·Cl-Na and HCO₃-Na type. ● F⁻ decreases with the increase of depth to water table. ● High fluoride is mainly affected by fluorine-containing minerals and weak alkaline. ● Fluorine pollution is mainly in the north near Laizhou Bay (wet season > dry season). ● Groundwater samples have a high F⁻ health risk (children > adults). Due to the unclear distribution characteristics and causes of fluoride in groundwater of Mihe-Weihe River Basin (China), there is a higher risk for the future development and utilization of groundwater. Therefore, based on the systematic sampling and analysis, the distribution features and enrichment mechanism for fluoride in groundwater were studied by the graphic method, hydrogeochemical modeling, the proportionality factor between conventional ions and factor analysis. The results show that the fluorine content in groundwater is generally on the high side, with a large area of medium-fluorine water (0.5–1.0 mg/L), and high-fluorine water is chiefly in the interfluvial lowlands and alluvial-marine plain, which mainly contains HCO₃·Cl-Na- and HCO₃-Na-type water. The vertical zonation characteristics of the fluorine content decrease with increasing depth to the water table. The high flouride groundwater during the wet season is chiefly controlled by the weathering and dissolution of fluorine-containing minerals, as well as the influence of rock weathering, evaporation and concentration. The weak alkaline environment that is rich in sodium and poor in calcium during the dry season is the main reason for the enrichment of fluorine. Finally, an integrated assessment model is established using rough set theory and an improved matter element extension model, and the level of groundwater pollution caused by fluoride in the Mihe-Weihe River Basin during the wet and dry seasons in the Shandong Peninsula is defined to show the necessity for local management measures to reduce the potential risks caused by groundwater quality.     

Decoding and quantitative detection of antibiotics by a luminescent mixed-lanthanide-organic framework

● A series of mixed-LOFs and portable LOF-fibers were synthesized. ● LOF-S3 was selected as a luminescent sensor for antibiotics. ● Mixed-LOF was capable of decoding antibiotics by emission intensity ratios. ● Linear relationship between antibiotic concentration and I545nm/I618nm was observed. Due to the potential risk of antibiotics to the environment, the development of inexpensive, simple, and reliable antibiotic detection methods is significant but also faces challenges. In this work, several lanthanide-organic frameworks (LOFs), constructed from lanthanide ions (Eu³⁺ and/or Tb³⁺) and 1,3,5-benzene-tricarboxylic acid (BTC), were synthesized by solvothermal method. LOF-S3 with comparable emission peaks of ⁵D₄ → ⁷F₅ (Tb³⁺, 545 nm) and ⁵D₀ → ⁷F₂ (Eu³⁺, 618 nm) was selected as a luminescent sensor. In this system, the highly efficient energy transferred from the organic linker to lanthanide ions and from Tb³⁺ to Eu³⁺ occurs. LOF-S3 sensor was capable of decoding antibiotics by distinguishable emission intensity ratios. Therefore, a two-dimensional decoded map of antibiotics was established. The linear relationship between antibiotic concentration and emission intensity ratio indicated the quantitative determination of antibiotics was feasible. As a typical analyte, the response mechanism of nalidixic acid (NA) was investigated in detail. The competition of NA and BTC for UV light absorption, as well as the binding propensity of NA and Tb, affected the organic linkers-to-lanthanide ions and Tb-to-Eu energy transfer, resulting in the change of fluorescence intensity ratio. The self-calibrating mixed-LOF sensor overcame the uncontrollable errors of the traditional absolute emission intensity method and generated stable luminescent signals in multiple cycles. Furthermore, the integration of LOF-S3 with polymer fibers enabled the formation of a LOF-polymer fibrous composite with fluorescence detection capability, which is a promising portable sensor for practical applications.