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Efficient carbon use is crucial for biological nitrogen removal. Traditional aerobic processes can waste carbon sources, exacerbating carbon deficiency. This study explores an anaerobic/oxic/anoxic system with sludge double recirculation to improve nitrogen removal in low C/N wastewater. This system integrated aerobic nitrification after the carbon intracellular storage, separating carbon and nitrogen by denitrifying glycogen-accumulating organisms (DGAOs) with endogenous partial denitrification and Anammox within the anoxic units. A significant efficiency of 91.02±7.01% chemical oxygen demand (COD) was converted into intracellular carbon in anaerobic units, significantly reducing carbon futile oxidation in the aerobic units by effectively separating COD from ammonia. Intracellular storage of carbon sources and microbial adaptation to carbon scarcity prevent futile oxidation of COD in the aerobic units even with short-term high dissolved oxygen (DO), thereby enhancing nitrogen removal under anoxic conditions with sufficient intracellular carbon source. The microbial analysis identified Candidatus Brocadia as the dominant anammox bacteria, in combination with the activity of DGAOs and other related microbial communities, accounting for 37.0% of the TN removal. Consequently, the system demonstrated remarkable nitrogen removal efficiencies, achieving 81.3±3.3% for total nitrogen (TN) and 98.5±0.9% for ammonia nitrogen while maintaining an effluent COD concentration of 17.2±9.1 mg/L, treating the low C/N of 4.18 in the influent wastewater. The findings in this study provide a sustainable and energy-saving technique for conventional WWTPs to meet strict discharge standards by avoiding futile oxidation of COD and encouraging anammox contributions.

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Nitrilotriacetic acid (NTA), a biodegradable chelant, has been promoted to effectively assist Pb phytoextraction, while a few researches available on the phytostabilizer of Athyrium wardii (Hook.). In this study, two incubation experiments and a subsequent column experiment were conducted to investigate the effects of application of NTA on Pb availability in soils and Pb accumulation in A. wardii and associated leaching risk. The application of NTA significantly increased the exchangeable Pb and Pb bound to carbonates along with a decreased pH, leading to enhanced Pb availability in soils. It was more effective in enhancing Pb availability in soils by adding 2 mmol kg-1 NTA into soils at once for 7 d, thus demonstrating potential for enhancing Pb uptake by A. wardii. After the addition of 2 mmol kg-1 NTA for 7 d, Pb concentrations in roots of A. wardii was enhanced by 23.8%, along with 10.6% of increase for Pb accumulation in roots. No significant changes were observed for the biomass of A. wardii. Meanwhile, the available Pb and TCLP-extractable Pb in 0-20 cm soils increased by 11.1-23.4% and 7.1-31.2%, thus promoting Pb leaching in 0-20 cm soils. However, there were no changes for Pb leaching risk levels of 20-40 cm soils. No Pb was detected in the leachates from all columns. The application of 2 mmol kg-1 NTA at once for 7 d is therefore proved to show greater potential in enhancing Pb remediation efficiency by the phytostabilizer of A. wardii without increasing Pb leaching risk into groundwater.

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Better understanding of microbial activity in the rhizosphere soils associated with lead (Pb) uptake by plants may help with the phytoremediation of Pb-contaminated soils. In this work, the effects of Pb exposure (0, 200, 400, 600, 800 mg kg-1) on Pb accumulation and soil microbial activity in the rhizosphere of the mining ecotype (ME) and corresponding non-mining ecotype (NME) of Athyrium wardii (Hook.) Makino were investigated through a pot experiment. Although the plant growth of the two ecotypes was inhibited under Pb stress, the ME showed a less biomass decrease (12.6-44.0%) for aboveground than the NME, showing a greater tolerance to Pb stress. Pb concentrations as well as Pb accumulation in the two ecotypes showed an increasing trend with increasing soil Pb concentrations. The ME presented greater Pb accumulation ability than the NME, especially in underground parts. Pb availability in the rhizosphere soils of the two ecotypes after harvest decreased compared with those before transplantation. Available Pb in the rhizosphere of the ME was 1.4-4.8 times higher than that of the NME under exposure to 200-800 mg kg-1 Pb. The ME shows a greater ability to mobilize Pb in the rhizosphere soils. Pb exposure resulted in an inhibition of microbial activity in the rhizosphere of the two ecotypes. The ME demonstrated greater soil respiration and microbial biomass carbon (MBC) in the rhizosphere than the NME when treated with 200-800 mg kg-1 Pb. The ME showed a less decrease for MBC and a less increase for metabolic quotient in the rhizosphere soils than the NME when exposed to Pb generally. Microorganisms in the rhizosphere soils of the ME seem to be much more adapted to Pb stress, thus showing a great benefit for Pb accumulation and the phytostabilization of Pb-contaminated soils by the ME.

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In order to deal with cadmium (Cd(II)) pollution, three modified biochar materials: alkaline treatment of biochar (BC-NaOH), KMnO4 impregnation of biochar (BC-MnOx) and FeCl3 magnetic treatment of biochar (BC-FeOx), were investigated. Nitrogen adsorption-desorption isotherms, Fourier transform infrared spectroscopy (FTIR), Boehm titration, and scanning electron microscopy (SEM) were used to determine the characteristics of adsorbents and explore the main adsorption mechanism. The results show that manganese oxide particles are carried successfully within the biochar, contributing to micropore creation, boosting specific surface area and forming innersphere complexes with oxygen-containing groups, while also increasing the number of oxygen-containing groups. The adsorption sites created by the loaded manganese oxide, rather than specific surface areas, play the most important roles in cadmium adsorption. Batch adsorption experiments demonstrate a Langmuir model fit for Cd(II), and BC-MnOx provided the highest sorption capacity (81.10 mg g-1). The sorption kinetics of Cd(II) on adsorbents follows pseudo-second-order kinetics and the adsorption rate of the BC-MnOx material was the highest (14.46 g (mg·h)-1). Therefore, biochar modification methods involving KMnO4 impregnation may provide effective ways of enhancing Cd(II) removal from aqueous solutions.

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To investigate the passivation of different modified biochars on the speciation and availability of cadmium contaminated soil, the modified biochars were treated by different approaches (acid/base treatment, impregnation with manganese oxides, magnetic modification) and biochars(BC) were used as soil passivating agents for soil culture experiments. The result indicated that the content of available cadmium decreased significantly by BC and modified biochars in originally contaminated soil. Compared with CK, the percentage of available cadmium in originally contaminated soil was reduced by more than 50% using impregnable biochars by KMnO4(BC-KMnO4) and basic biochars by NaOH(BC-NaOH). And the content of available cadmium decreased significantly by three modified biochars which were BC-KMnO4, BC-NaOH and FeCl3 magnetization biochars(BC-FeCl3) in exogenously contaminated soil. Particularly, the best performance was observed with BC-KMnO4 that reduced 30% available cadmium in exogenously contaminated soil. However, the passivation of BC was not significant, and the content of available cadmium slightly increased (3.8%-24.5%) by BC-HNO3 in exogenously contaminated soil. Furthermore, the content of exchangeable cadmium was increased by 20.2% with 2.5% BC-HNO3 in exogenously contaminated soil, while significantly decreased by other modified biochars and BC, and the 10% BC-KMnO4 reduced 65.1% exchangeable cadmium in originally contaminated soil. Meanwhile, soil pH was increased significantly by BC, BC-KMnO4 and BC-NaOH, while was reduced by BC-HNO3. The contents of organic carbon and exchangeable base cations in soil were improved by all the treatments. The results of regression analysis showed that the content of available cadmium in originally contaminated soil was significantly negatively correlated with soil pH, soil exchangeable Na+, while the content of available cadmium in exogenously contaminated soil was significantly negatively correlated with soil pH, soil organic carbon, soil exchangeable Mg2+, Na+, K+. Accordingly, the lower available cadmium in contaminated soil may correlate with the increasing content of organic carbon, exchangeable base cations and pH. In summary, the materials of BC-KMnO4 could be used as a superior passivating agent for in situ remediation of cadmium pollution, while the materials of BC-HNO3 could slightly activate cadmium in the soil, leading to some risk in in situ remediation.

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