Metal behavior and soil quality changes induced by the application of tailor-made combined biochar: An investigation at pore water scale.

The remediation performance of biochar varies based on the biomass used for its production. Further innovation involves developing tailor-made biochar by combining different raw materials to compensate for the limitations of pure biochar. Therefore, tailor-made combined biochar produced from the co-pyrolysis of pig manure and invasive Japanese knotweed (P1J1), as well as biochars produced from these feedstocks separately, i.e., pure pig manure (PM) and pure Japanese knotweed (JK), were applied to Pb and As contaminated soil to evaluate the biochar-induced changes on soil properties, microbial activity, DOM, and metal and metalloids solubility at the soil pore water scale. Biochar application reduced soluble Pb, whereas enhanced the As mobility; the increased soil pH after biochar addition played a fundamental role in reducing the Pb solubility, as revealed by their significant negative correlation (r = -0.990, p < 0.01). In contrast, the release of dissolved P strongly influenced As mobilization (r = 0.949, p < 0.01), especially in P-rich PM and P1J1 treatments, while JK showed a marginal effect in mobilizing As. Soils treated with PM, P1J1, and JK mainly increased Gram-negative bacteria by 56 %, 52 %, and 50 %, respectively, compared to the control. Fluorescence excitation-emission matrix spectroscopy combined with parallel factor analysis identified three components in pore water DOM, C1 (long wavelength humic-like), C2 (short wavelength humic-like), and C3 (protein-like), which were dominant respectively in the P1J1, JK, and PM-added soil. A principal component analysis (PCA) confirmed that the PM and P1J1 had similar performance and were more associated with releasing P and Mg and specific DOM components (C1 and C3). Meanwhile, P1J1 supplemented soil OM/OC and K, similar to JK. The results of this study suggest that combined biochar P1J1 can comprehensively enhance soil quality, embodying the advantages of pure PM and JK biochar while overcoming their shortcomings.

Degradation of micropollutants in secondary wastewater effluent using nonthermal plasma-based AOPs: The roles of free radicals and molecular oxidants.

Emerging micropollutants (µPs) appearing in water bodies endanger aquatic animals, plants, microorganisms and humans. The nonthermal plasma-based advanced oxidation process is a promising technology for eliminating µPs in wastewater but still needs further development in view of full-scale industrial application. A novel cascade reactor design which consists of an ozonation chamber preceding a dielectric barrier discharge (DBD) plasma reactor with a falling water film on an activated carbon textile (Zorflex®) was used to remove a selection of µPs from secondary municipal wastewater effluent. Compare to previous plasma reactor, molecular oxidants degraded micropollutants again in an ozonation chamber in this study, and the utilization of different reactive oxygen species (ROS) was improved. A gas flow rate of 0.4 standard liter per minute (SLM), a water flow rate of 100 mL min-1, and a discharge power of 25 W are identified as the optimal plasma reactor parameters, and the µP degradation efficiency and electrical energy per order value (EE/O) are 84-98% and 2.4-5.3 kW/m³, respectively. The presence of ROS during plasma treatment was determined in view of the µPs removal mechanisms. The degradation of diuron (DIU), bisphenol A (BPA) and 2-n-octyl-4-isothiazolin-3-one (OIT) was mainly performed in ozonation chamber, while the degradation of atrazine (ATZ), alachlor (ALA) and primidone (PRD) occurred in entire cascade system. The ROS not only degrade the µPs, but also remove nitrite (90.5%), nitrate (69.6%), ammonium (39.6%) and bulk organics (11.4%). This study provides insights and optimal settings for an energy-efficient removal of µPs from secondary effluent using both free radicals and molecular oxidants generated by the plasma in view of full-scale application.

Advanced treatment of landfill leachate through combined Anammox-based biotreatment, O3/H2O2 oxidation, and activated carbon adsorption: technical performance, surrogate-based control strategy, and operational cost analysis.

The complexity of landfill leachate makes it difficult to treat it with a single biological/ physical/chemical process. Moreover, the dynamic leachate characteristics pose a challenge for effective process control. Therefore, a combined treatment, consisting of a one-stage partial nitrification-Anammox process, an O3/H2O2 process, and a granular activated carbon filtration (GAC) process, was investigated. Meanwhile, a novel surrogate-based ozone dose control strategy for O3/H2O2 process was evaluated. Results show that this three-stage process offers high removal of total nitrogen (> 90%), COD (chemical oxygen demand, 60-82%), and micropollutants (atrazine, alachlor, carbamazepine, and bisphenol A, > 96%), satisfying discharge requirements. In the combined post-treatment, ozone dosing for COD removal can be real-time controlled by UVA254 reduction monitoring, based on a specific correlation between COD and UVA254 changes. On the other hand, O3/H2O2 pre-treatment controlled at a 50% UVA254 reduction shows to be the optimal point, when adsorption is designed as the main step for COD removal. Cost analysis shows that post-treatment with low (high) organic load i.e., COD ≤ (≥)540 mg/L, a combination with O3/H2O2 (GAC) as the main step appears to be more cost-effective. Therefore, a dynamic operation strategy in response to the leachate change is recommended.

Surrogate-based follow-up of activated carbon adsorption preceded by ozonation for removal of bulk organics and micropollutants from landfill leachate.

Although combined ozonation with activated carbon (AC) adsorption is a promising technique for leachate treatment, little is known about how ozone-induced changes in leachate characteristics affect the organics adsorption, especially in view of emerging micropollutants (MPs) removal. Furthermore, the online monitoring of MPs is challenging but desirable for efficient treatment operation. This study investigates how preceding ozonation impacts the adsorption of bulk organics (expressed as chemical oxygen demand (COD)) and ozone-recalcitrant MPs, i.e., primidone, atrazine and alachlor, in leachate using batch and column adsorption tests. Additionally, a new surrogate-based model was evaluated for predicting MPs breakthrough. Batch tests revealed that ozonation results in a decreasing apparent affinity of COD towards AC, but the non-adsorbable part did not obviously change. The adsorption of MPs in ozonated leachate was (1-41%) higher than that in non-ozonated leachate, especially for the more hydrophobic alachlor and atrazine, due to a reduced sites competition from bulk organics. Column adsorption showed that ozonation delayed COD and MPs breakthrough due to the reduced COD loading and sites competition, respectively. An increased empty bed contact time (EBCT, 10-40 min) led to an increased COD uptake by a factor of 3.0-3.2 for ozonated and non-ozonated leachates, while MPs adsorption also increased, suggesting that pore blockage rather than site competition could be the dominant inhibitory effect. The data from column adsorption demonstrate the applicability of developed surrogate-based model for predicting MPs breakthrough. Particularly, the fitting parameters were not affected by change of leachate characteristics, while they were impacted by change of EBCT.

Intensified ozonation in packed bubble columns for water treatment: Focus on mass transfer and humic acids removal.

Ozonation has been widely applied for the oxidation of contaminants in wastewater, and the disinfection of water. However, low ozone (O3) mass transfer efficiency in common ozonation reactors requires high O3 doses and causes high energy consumption. In this study, to intensify the O3 mass transfer and oxidation of humic acids (HA) solution, a lava rock packed bubble column (LBC) and a metal pall ring packed bubble column (MBC) were developed and evaluated. In comparison with non-packed bubble column (BC), both LBC and MBC enhanced the O3 mass transfer efficiency and the generation of hydroxyl radicals, thereby increasing the HA removal from an aqueous solution. At applied O3 dose of 33.3 mg/(Lcolumn h), the HA removal efficiency in BC was only 47%. When MBC and LBC were applied, it increased to 66% and 72%, respectively. Meanwhile, the O3 utilization efficiency in LBC reached 68%, which was higher than that in MBC (50%) and BC (21%). Consequently, LBC has the lowest energy consumption (EEO) for HA removal (1.4 kWh/m3), followed by MBC (1.6 kWh/m3) and BC (2.9 kWh/m3). LBC had better performance than MBC due to the adsorptive and catalytic roles of lava rock on the ozonation process. This study demonstrates the advantages of using lava rocks as packed materials in O3 bubble column over metal pall rings in intensifying O3 mass transfer and organic matters removal, which provides some insights into promoting the industrial application of O3.

Characterization of landfill leachate by spectral-based surrogate measurements during a combination of different biological processes and activated carbon adsorption.

Surrogate measurements based on excitation-emission matrix fluorescence spectra (EEMs) and ultraviolet-visible absorption spectra (UV-vis) were used to monitor the evolution of dissolved organic matter (DOM) in landfill leachate during a combination of biological and physical-chemical treatment consisting of partial nitritation-anammox (PN-Anammox) or nitrification-denitrification (N-DN) combined with granular active carbon adsorption (GAC). PN-Anammox resulted in higher nitrogen removal (81%), whereas N-DN required addition of an external carbon source to increase nitrogen removal from 24% to 56%. Four DOM components (C1 to C4) were identified by excitation-emission matrix-parallel factor analysis (EEM-PARAFAC). N-DN showed a greater ability to remove humic-like components (C1 and C3), while the protein-like component (C4) was better removed by PN-Anammox. Both biological treatment processes showed limited removal of the medium molecular humic-like component (C2). In addition, the synergistic effect of biological treatments and adsorption was studied. The combination of PN-Anammox and GAC adsorption could remove C4 completely and also showed a good removal efficiency for C1 and C2. The Thomas model of adsorption revealed that GAC had the maximum adsorption capacity for PN-Anammox treated leachate. This study demonstrated better removal of nitrogen and fluorescence DOM by a combination of PN-Anammox and GAC adsorption, and provides practical and technical support for improved landfill leachate treatment.

Pilot study of nitrogen removal from landfill leachate by stable nitritation-denitrification based on zeolite biological aerated filter.

A pilot (about 1 m3/d) process consisting of pre-denitrification and zeolite biological aerated filter (ZBAF) was established and run for nitrogen removal of landfill leachate. The results showed that stable nitritation and denitrification was achieved for landfill leachate with removal efficiency of Chemical Oxygen Demand (CODCr), ammonium and total nitrogen (TN) of 53.2 ±â€¯3.0%, 93.5 ±â€¯2.4% and 74.7 ±â€¯9.4%, respectively. Based on the ammonium adsorption equilibrium by zeolite, stable free ammonia could be maintained for inhibition of nitrite oxidizing bacteria (NOB) and dominance of ammonia oxidizing bacteria (AOB) in ZBAF, resulting in efficient nitritation with a nitrite accumulation ratio higher than 90.0% and an average nitrite production rate of 1.387 kg NO2--N m-3 day-1. High-throughput sequencing analysis further revealed enrichment of AOB and elimination of NOB in ZBAF. Compared to two-stage anoxic-oxic process, the pilot-scale process could save approximate 5000 mg/L glucose (about 3.10 US dollar/m3) with almost similar TN removal performance. All results obtained demonstrated the feasibility of the pilot process, which might be highly promising for the nitritation and denitrification of low C/N landfill leachate in the future.

Partial nitrification performance and mechanism of zeolite biological aerated filter for ammonium wastewater treatment.

A zeolite biological aerated filter (ZBAF) with continuous feeding was successfully applied for achieving stable partial nitrification. Excellent nitrite accumulation (higher than 98.0%) and high nitrite/nitrate production rate (NPR) (approximately 0.760kg/m3/d) were obtained with increase influent ammonium concentration from 250 to 550mg/L within a nitrogen loading rate (NLR) of 0.854-1.200kg/m3/d. Owning to the adsorption of zeolite to ammonium, free ammonia (FA) concentration could remain at an appropriate range for inhibition of nitrite oxidizing bacteria (NOB) and dominance of ammonia-oxidizing bacteria (AOB), which should be responsible for the excellent partial nitrification realized in ZBAF. Kinetic study showed that the production of nitrite in ZBAF followed the zero-order kinetics model and high-throughput sequencing analysis further presented the enrichment of AOB and inhibition of NOB in ZBAF. All the results demonstrated that ZBAF hold a great potential in the application of partial nitrification for ammonium wastewater treatment.

Partial nitrification and denitrification of mature landfill leachate using a pilot-scale continuous activated sludge process at low dissolved oxygen.

Controlling of low dissolved oxygen (DO) levels (0.1-0.5mg/L), a cost-effective strategy, was applied to a pilot-scale anoxic-oxic-oxic-anoxic process for partial nitrification and denitrification of mature landfill leachate. High ammonium removal efficiency, stable nitrite accumulation rate and total nitrogen removal efficiency was higher than 95.0%, 90.0% and 66.4%, respectively, implying potential application of this process for nitrogen removal of mature landfill leachate. Efficient nitrite accumulation in the first oxic reactor depended on low DO conditions and sufficient alkalinity. However, operational limit was mainly decided by actual hydraulic retention time (AHRT) of the first oxic reactor and appeared with AHRT less than 13.9h under DO of 0.3-0.5mg/L. High-throughput sequencing analysis demonstrated significant change of bacterial diversity in the first oxic reactor after a long-term operation and dominant bacteria genus Nitrosomonas was shown to be responsible for NH4(+)-N removal and nitrite accumulation under low DO levels.