Elucidating distinct roles of chemical reduction and autotrophic denitrification driven by three iron-based materials in nitrate removal from low carbon-to-nitrogen ratio wastewater.

Effective nitrate removal is a key challenge when treating low carbon-to-nitrogen ratio wastewater. How to select an effective inorganic electron donor to improve the autotrophic denitrification of nitrate nitrogen has become an area of intense research. In this study, the nitrate removal mechanism of three iron-based materials in the presence and absence of microorganisms was investigated with Fe2+/Fe0 as an electron donor and nitrate as an electron acceptor, and the relationship between the iron materials and denitrifying microorganisms was explored. The results indicated that the nitrogen removal efficiency of each iron-based material coupled sludge systems was higher than that of iron-based material. Furthermore, compared with the sponge iron coupled sludge system (60.6%-70.4%) and magnetite coupled sludge (56.1%-65.3%), the pyrite coupled sludge system had the highest removal efficiency of TN, and the removal efficiency increased from 62.5% to 82.1% with time. The test results of scanning electron microscope, X-ray photoelectron spectroscopy and X-ray diffraction indicated that iron-based materials promoted the attachment of microorganisms and the chemical reduction of nitrate in three iron-based material coupled sludge systems. Furthermore, the pyrite coupled sludge system had the highest nitrite reductase activity and can induce microorganisms to secrete more extracellular polymer substances. Combined with high-throughput sequencing and PICRUSt2 functional predictive analysis software, the total relative abundance of the dominant bacterial in pyrite coupled sludge system was the highest (72.06%) compared with the other iron-based material systems, and the abundance of Blastocatellaceae was relatively high. Overall, these results suggest that the pyrite coupled sludge system was more conducive to long-term stable nitrate removal.

Autotrophic denitrification by sulfur-based immobilized electron donor for enhanced nitrogen removal: Denitrification performance, microbial interspecific interaction and functional traits.

Sulfur-driven autotrophic denitrification (SdAD) is a promising nitrogen removing process, but its applications were generally constrained by conventional electron donors (i.e., thiosulfate (Na2S2O3)) with high valence and limited bioavailability. Herein, an immobilized electron donor by loading elemental sulfur on the surface of polyurethane foam (PFSF) was developed, and its feasibility for SdAD was investigated. The denitrification efficiency of PFSF was 97.3%, higher than that of Na2S2O3 (91.1%). Functional microorganisms (i.e., Thiobacillus and Sulfurimonas) and their metabolic activities (i.e., nir and nor) were substantially enhanced by PFSF. PFSF resulted in the enrichment of sulfate-reducing bacteria, which can reduce sulfate (SO42-). It attenuated the inhibitory effect of SO42-, whereas the generated product (hydrogen sulfide) also served as an electron donor for SdAD. According to the economic evaluation, PFSF exhibited strong market potential. This study proposes an efficient and low-cost immobilized electron donor for SdAD and provides theoretical support to its practical applications.

Research advances on impacts micro/nanoplastics and their carried pollutants on algae in aquatic ecosystems: A review.

The widespread presence of micro/nanoplastics in aquatic ecosystems has certainly affected ecosystem functions and food chains/webs. The impact is worsened by the accumulation of different pollutants and microorganisms on the surface of microplastics. At the tissue, cellular, and molecular levels, micro/nanoplastics and the contaminants they carry can cause damage to aquatic organisms. Problematically, the toxic mechanism of micro/nanoplastics and contaminants on aquatic organisms is still not fully understood. Algae are key organisms in the aquatic ecosystem, serving as primary producers. The investigation of the toxic effects and mechanisms of micro/nanoparticles and pollutants on algae can contribute to understanding the impact on the aquatic ecosystem. Micro/nanoplastics inhibit algal growth, reduce chlorophyll and photosynthesis, induce ultrastructural changes, and affect gene expression in algae. The effects of energy flow can alter the productivity of aquatic organisms. The type, particle size, and concentration of micro/nanoparticles can influence their toxic effects on algae. Although there has been some research on the toxic effects of algae, the limited information has led to a significant lack of understanding of the underlying mechanisms. This paper provides a comprehensive review of the interactions between micro/nanoplastics, pollutants, and algae. The effects of various factors on algal toxicity are also analyzed. In addition, this article discusses the combined effects of microplastics, global warming, and oil pollution on algae and aquatic ecosystems in the context of global change. This research is of great importance for predicting future environmental changes. This review offers a more comprehensive understanding of the interactions between microplastics/nanoplastics and algae, as well as their impact on the carbon cycle.

Selective adsorption of tetracycline and copper(II) on ion-imprinted porous alginate microspheres: performance and potential mechanisms.

A novel epichlorohydrin and thiourea grafted porous alginate adsorbent (UA-Ca/IIP) was synthesized using ion-imprinting and direct templating to remove copper ions (Cu(II)) and tetracycline (TC) in aqueous solution. UA-Ca/IIP demonstrated great selectivity for Cu(II) and TC among different coexisting anions (CO32-, PO43- and SO42-), cations (Ca2+, Mg2+ and NH4+), and antibiotics (oxytetracycline and sulfamethoxazole). The adsorption of TC and Cu(II) by UA-Ca/IIP was significantly affected by the pH of the solution, and the quantity of TC and Cu(II) adsorbed reached a maximum at pH 5. A pseudo-second-order model better fitted the kinetic data; the Langmuir model predicted the maximum adsorption quantities 3.527 mmol TC g-1 and 4.478 mmol Cu(II) g-1 at 298 K. Thermodynamic studies indicated that the TC and Cu(II) adsorption was more rapid at a higher temperature. Antagonistic and synergistic adsorption experiments showed that the adsorption capacity of TC would increase significantly with the increase of Cu(II) concentration. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy indicated that along with the influence of pH, electrostatic interaction and complexation were the main mechanisms of TC and Cu(II) adsorption. Regeneration experiments revealed that TC and Cu(II) were removed efficiently and that UA-Ca/IIP was recyclable over the long term. These results show that the modified porous alginate microsphere is a green and recyclable adsorbent, which has good selectivity and high adsorption performance for the removal of TC and Cu(II).

Performance and mechanisms of urea exposure for enhancement of biotransformation of sewage sludge into volatile fatty acids.

Herein, a cost-effective method for improving the anaerobic fermentation performance of sewage sludge (SS) is proposed. The highest volatile fatty acids (VFAs) reached up to 5550 mg COD/L with the supplementation of 0.2 g urea/g total suspended solids (TSS). Intensive exploration showed that SS decomposition was profoundly triggered by urea and the free ammonia generated due to the hydrolysis of urea, providing adequately bioaccessible substrates for acidogenic reactions and thus contributing to VFAs formation. Microbial composition analysis indicated that functional bacteria (i.e., Tissierella and Clostridium) associated with VFAs generation were enriched. Moreover, the metabolic activities of functional flora (i.e., membrane transport and fatty acid synthesis) were up-regulated due to the stimulation of urea. In general, the increase in bioavailable organic matter and functional microbes, and thus the increased microbial metabolic activities, improved the efficient production of VFAs. This study could provide a cost-effective approach for resource recovery from SS.

Recent advances on micro/nanoplastic pollution and membrane fouling during water treatment: A review.

Effluent from sewage treatment plant, as an important source of microplastics (MPs) in receiving water, has attracted extensive attention. Membrane separation process shows good microplastic removal performance in the existing tertiary water treatment process. Problematically, membrane fouling and insufficient removal of small organic molecules are still the key obstacles to its further extensive application. Dissolved organics, extracellular polymers and suspended particles in the influent are deposited on the membrane surface and internal structure, reducing the number and pore diameter of effective membrane aperture, and increasing the resistance of membrane filtration. Exploring the mechanism and approach of membrane fouling caused by micro/nanoplastics is the key to alleviate fouling and allow membranes to operate longer. In this paper, removal performance of micro/nanoplastics by current membrane filtration and the contribution to membrane fouling during water treatment are thoroughly reviewed. The coupling mechanisms between micro/nanoplastics and other pollutants and mechanism of membrane fouling caused by composite micro/nanoplastics are discussed. Additionally, on this basis, the prospect of combined process for micro/nanoplastic removal and membrane fouling prevention is also proposed and discussed, which provides a valuable reference for the preferential removal of micro/nanoplastics and development of antifouling membrane.

Controllable synthesis of Co-Al layered double hydroxides with different anionic intercalation layers for the efficient removal of methyl orange.

In order to investigate the effect of the types of interlayer anions on the adsorption performance of LDHs, herein, we synthesized three cobalt-aluminum layered double hydroxides (CoAl-LDHs) with different interlayer anions (NO3-/Cl-/CO32-). The experimental results demonstrate that the CoAl-LDH (Cl-) exhibited high adsorption capacity of 1372.1 mg/g at room temperature and the fastest adsorption rate on methyl orange (MO), mainly attributed to the excellent ion exchange capacity and high specific surface area and pore volume. Furthermore, the ion exchange driven by electrostatic interaction, hydrogen bonding, and surface complexation might be the main mechanisms for MO adsorption on CoAl-LDH (Cl-) and CoAl-LDH (NO3-). However, the MO adsorption on CoAl-LDH (CO32-) was strongly pH-dependent and the optimal pH value was about 3.5. Additionally, the supramolecular structure of CoAl-LDHs-MO was formed through electrostatic interaction, hydrogen bonding, and surface complexation between the host hydroxide layers and the guest MO- after adsorption equilibrium. An in-depth understanding of the differences in the adsorption performance of three anion-intercalated CoAl-LDHs will provide opportunities for further improvement of the adsorption capacity and exhibit a bright future for the design and optimization of efficient nano-adsorbents shortly.

Insights into the formation of environmentally persistent free radicals during photocatalytic degradation processes of ceftriaxone sodium by ZnO/ZnIn2S4.

At present, the researches on photocatalysis were mainly focused on the design, improvement and development of catalysts, and less attention was paid to the existing characteristics of environmentally persistent free radicals (EPFRs) during the process of photocatalytic oxidation. In this study, A flower-like Z-type heterojunction ZnO/ZnIn2S4 (ZnO/ZIS) and typical antibiotic ceftriaxone sodium (CS) were taken as study objects, concentrating on the generation characteristics of EPFRs during the degradation of CS by ZnO/ZIS, and clarifying the degradation mechanism of CS in which EPFRs participated. The results showed that the degradation efficiency of 10 mg/L CS by 0.40 g/L ZnO/ZIS reached 85.3% in 150 min under the irradiation of 500 W xenon lamp. It was clear that ·O2- and h+ play major roles in CS degradation by ZnO/ZIS under visible light, and ·OH plays an auxiliary role. Furthermore, the formation mechanism of EPFRs during photocatalytic degradation processes of CS by ZnO/ZIS were first investigated thoroughly via experimental analysis and density functional theory (DFT) calculations. The concentration level of EPFRs centered on oxygen atoms is 1011 spin/mm3, which were generated in the process of degradation of CS by ZnO/ZIS under visible light. The production of EPFRs chiefly includes two procedures: chemical adsorption and transfer of electrons. The adsorption energy of precursor P8 on ZnIn2S4 side is -1.91 eV, the electrons transferred from precursor P8 and P11 to ZnO/ZnIn2S4 heterojunction. Surprisingly, EPFRs have little negative effects on the degradation process of CS by ZnO/ZIS. The study was not only a key field in the development of photocatalysis technology, but also a new way to study the removal mechanism of antibiotics.

Re-circulation of Fe/persulfate regulated sludge fermentation products for sewage treatment: Focus on pollutant removal efficiency, microbial community and metabolic activity.

Persulfate (PS)-based technologies have been demonstrated as efficient methods for enhancing the performance of waste activated sludge (WAS) anaerobic fermentation. Except for volatile fatty acids (VFAs), however, some exogenous substances would be also released during this process, which might affect its application as a carbon source for sewage treatment. To fill this knowledge gap, the feasibility of sludge fermentation liquid regulated by Fe/persulfate (PS) (PS-FL) as a carbon source for sewage treatment was investigated in this study. Results indicated that PS-FL exhibits distinct effects on the pollutants removal compared with commercial sodium acetate. It facilitates PO43--P removal but slightly inhibited COD removal & denitrification, and sludge settleability was also decreased. The mechanistic analysis demonstrated that PS-FL could stimulate the enrichment of phosphorus-accumulating bacteria (i.e. Candidatus Accumulibacter) and the enhancement of their metabolic activities (i.e. PKK), thereby enhancing the biological PO43--P removal. Moreover, Fe ions in PS-FL could combine with PO43--P to form a precipitate and thus further contributed to PO43--P removal. Conversely, the sulfate reduction process induced by SO42- in PS-FL inhibits denitrification by reducing the abundance of denitrifying bacteria (i.e. Dechloromonas) and metabolic activities (i.e. narG). Additionally, PS-FL also decreased the abundance of flocculation bacteria (i.e. Flavobacterium) and down-regulated the expression of functional genes responsible for COD removal, by which it exhibited certain negative effects on COD removal and sludge settleability. Overall, this work demonstrated that PS-FL can re-circulation as a carbon source for sewage treatment, which provides a new approach to recovering valuable carbon sources from WAS.

Efficient degradation of sulfamethoxazole under visible light irradiation by polyaniline/copper sulfide composite photocatalyst.

A novel composite photocatalyst polyaniline/copper sulfide (PANI/CuS) was successfully prepared using an in situ precipitation method. The surface morphology, internal structure, thermal stability, electronegativity, and visible light photocatalytic activity of PANI/CuS were analyzed by a series of characterization methods. Sulfamethoxazole (SMX) was used as the representative pollutant; the degradation effect, degradation kinetic, and influencing factor of SMX by PANI/CuS under visible light were systematically investigated. The degradation mechanism of SMX by PANI/CuS was explained by a series of free radical quenching experiments and electron paramagnetic resonance spectroscopy experiments. The following were the main conclusions through the above research. First, the degradation effect of SMX by composite PANI/CuS was better than that by pure CuS under the same experimental conditions, which indirectly proved that the addition of PANI could effectively delay the photochemical corrosion of CuS. Next, when the dosage of PANI/CuS was 0.04 g/L, initial concentration of SMX was 5 ppm, pH was 2.0, and the simulated visible light was 500 W, the degradation effect of SMX was as high as 72.13%. Last, the hole (h+) played a major role and the superoxide radical (·O2-) played an auxiliary role in the degradation process of SMX by PANI/CuS; persistent free radicals exist simultaneously.

Sludge-based activated carbon catalyzed H2O2 oxidation of reactive azo dyes.

Sludge-based activated carbon (ZAC) was successfully employed as both adsorbent and catalyst for the oxidation process of reactive yellow 86 (RY86) and reactive black 5 (RB5). Physicochemical properties of the prepared sewage sludge-derived activated carbon were evaluated by N2 adsorption/desorption, Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The effects of parameters such as initial pH, H2O2 concentrations, ZAC dosages, dye concentrations and temperature on the removal of RY86 and RB5 were investigated. Kinetics results showed that the adsorption rates of RY86 and RB5 by ZAC can be approximated by the pseudo-first order model, and that the oxidation rates by Behnajady-Modirshahla-Ghanbery (BMG) model. Under the optimum conditions in the experiment, i.e. pH = 6.0, T = 303 K, [H2O2] = 49.5 mmol/L, [ZAC] = 4 g/L, [dyes] = 300 mg/L and t = 150 min, 99%, 88% and 84% of colour, COD and TOC were removed by Fenton -like oxidation for RY86, while for RB5, the three removal rates were 90%, 70% and 62%, respectively, indicating that sludge-based activated carbon can be used as an effective catalyst to oxidation of dyes by H2O2 from coloured wastewater.

The toxicity of virgin and UV-aged PVC microplastics on the growth of freshwater algae Chlamydomonas reinhardtii.

Although more attention has been paid to plastic pollution in marine ecosystems, research on the influence of plastic in freshwater ecosystems remains limited. To help fill this information gap, this article represents an investigation of the effects of virgin polyvinyl chloride (v-PVC) microplastics (MPs) and UV-aged polyvinyl chloride (a-PVC) MPs on the growth and chlorophyll content of the freshwater algae, Chlamydomonas reinhardtii (C. reinhardtii) at different periods (0, 24, 48, 72 and 96 h). The results suggest that both virgin and aged PVC MPs have negative effects on the growth of C. reinhardtii in the range of 10 mg/L to 200 mg/L, which leads to the reduction of chlorophyll-a level in the cells. Furthermore, a-PVC MPs were more toxic than v-PVC MPs, as shown by the a-PVC MPs' lower EC50 values after 96 h (63.66 mg/L for a-PVC MPs and 104.93 mg/L for v-PVC MPs). The inhibition effect of both kinds of PVC was also testified by the enhancement of enzymatic activity of superoxide dismutase (SOD) and malondialdehyde (MDA) in algae. Meanwhile, a-PVC MPs obviously had a higher toxicity than v-PVC MPs. The aging process that affected the surface characteristics of a-PVC was identified using Fourier transform infrared (FTIR) and Zetasizer. The carbonyl groups formed on the surface and the increased zeta potential of the a-PVC MPs affected the interaction between the microplastics and the algae, which increased the toxicity of aged microplastics. The research results presented here provide more evidence of the risks microplastics bring into the freshwater ecosystem.

The adsorption behavior of metals in aqueous solution by microplastics effected by UV radiation.

Microplastics are considered as the carrier to heavy metals in the environment. But the sorption ability of microplastics influenced by photo-aging is remaining unclear. In the present study, the sorption of two kinds of metal ions (Cu2+ and Zn2+) in the aqueous solution by both the virgin and aged microplastics was investigated. Polyethylene terephthalate (PET) debris, one of the typical kinds of microplastics was chosen in this study. Photo-aging of microplastics in environment was simulated using UV radiation in the laboratory. Date analysis indicated that the aged microplastics had higher adsorption capacity of heavy metals than original ones. This could be related to the increased surface area and oxygen containing function appeared in the surface of aged microplastics after UV radiation. When prolonging the time of radiation, the enhanced adsorption capacities of microplastics appeared for Cu2+ and Zn2+. These results showed a great interaction between the aging degree of plastics and sorption capacity to heavy metals. Meanwhile, external conditions including temperature and pH value were also showed great influence to the adsorption behavior.