Copper-based Ruddlesden-Popper perovskite oxides activated hydrogen peroxide for coal pyrolysis wastewater (CPW) degradation: Performance and mechanism.

Coal pyrolysis wastewater (CPW) contained all kinds of toxic and harmful components, which would seriously threaten the natural environment and human health. However, the traditional advanced oxidation processes frequently failed to remove phenolic substances. An A2BO4-type perovskite (La2CuO4) was successfully synthesized through sol-gel process and first applied in the treatment of CPW. More than 90% of 3, 5-dimethylphenol (DMP) was removed within 200 min at neutral conditions. Moreover, La2CuO4 also displayed excellent catalytic activity and stability in the actual CPW treatment process. Results demonstrated that DMP was removed through the attack of ∙OH, ∙O2- and 1O2 in La2CuO4/H2O2 system. The La2CuO4 were more favorable for H2O2 activation and have a lower adsorption energy than LaFeO3. XPS of fresh and spent La2CuO4 illustrated that the decomposition of hydrogen peroxide (H2O2) was mainly due to the redox cycle between surface copper and oxygen species. Moreover, the possible degradation pathway of DMP was deduced by identifying degradation products and analyzing density functional theory (DFT) calculations. This research provided a novel strategy for the development of perovskite-based catalytic materials on the treatment of practical CPW.

A novel study for joint toxicity of typical aromatic compounds in coal pyrolysis wastewater by Tetrahymena thermophile.

The coal pyrolysis wastewater (CPW) contributed to aquatic environment contamination with amount of aromatic pollutants, and the research on joint toxicity of the mixture of aromatic compounds was vital for environmental protection. By using Tetrahymena thermophile as non-target organism, the joint toxicity of typical nonpolar narcotics and polar narcotics in CPW was investigated. The results demonstrated that the nonpolar narcotics exerted chronic and reversible toxicity by hydrophobicity-based membrane perturbation, while polar narcotics performed acute toxicity by irreversible damage of cells. As the most hydrophobic nonpolar narcotics, indole and naphthalene caused the highest joint toxicity in 24 h with the lowest EC50mix (24.93 mg/L). For phenolic compounds, the combination of p-cresol and p-nitrophenol also showed the top toxicity (EC50mix = 10.9 mg/L) with relation to high hydrophobicity, and the joint toxicity was obviously stronger and more acute than that of nonpolar narcotics. Furthermore, by studying the joint toxicity of nonpolar narcotics and polar narcotics, the hydrophobicity-based membrane perturbation was the first step of toxicity effects, and afterwards the acute toxicity induced by electrophilic polar substituents of phenols dominated joint toxicity afterwards. This toxicity investigation was critical for understanding universal and specific effects of CPW to aquatic organisms.

Effects of methanol, sodium citrate, and chlorella powder on enhanced anaerobic treatment of coal pyrolysis wastewater.

To better promote environment friendly development of the coal chemical industry, this study investigated effects of methanol, sodium citrate, and chlorella powder (a type of microalgae) as co-metabolic substances on enhanced anaerobic treatment of coal pyrolysis wastewater with anaerobic sludge. The anaerobic sludge was loaded into four 2 L anaerobic reactors for co-metabolism enhanced anaerobic experiments. Anaerobic reactor 1 (R1) as control group did not add a co-metabolic substance; anaerobic reactor 2 (R2) added methanol; anaerobic reactor 3 (R3) added sodium citrate; and anaerobic reactor 4 (R4) added chlorella powder. In the blank control group, the removal ratios of total phenol (TPh), quinoline, and indole were only 12.07%, 42.15%, and 50.47%, respectively, indicating that 50 mg/L quinoline, 50 mg/L indole, and 600 mg/L TPh produced strong toxicity inhibition function on the anaerobic microorganism in reactor. When the concentration of methanol, sodium citrate, and chlorella was 400 µg/L, the reactors with co-metabolic substances had better treatment effect on TPh. Among them, the strengthening effects of sodium citrate (TPh removal ratio: 44.87%) and chlorella (47.85%) were better than that of methanol (38.72%) and the control group (10.62%). Additionally, the reactors with co-metabolic substances had higher degradation ratios on quinoline, indole, and chemical oxygen demand (COD). The data of extracellular polymeric substances showed that with the co-metabolic substances, anaerobic microorganisms produced more humic acids by degrading phenols and nitrogen-containing heterocyclic compounds (NHCs). Compared with the control group, the reactors added with sodium citrate and chlorella had larger average particle size of sludge. Thus, sodium citrate and chlorella could improve sludge sedimentation performance by increasing the sludge particle size. The bacterial community structures of reactors were explored and the results showed that Aminicenantes genera incertae sedis, Levinea, Geobacter, Smithella, Brachymonas, and Longilinea were the main functional bacteria in reactor added with chlorella.

Metagenomic analysis of aromatic ring-cleavage mechanism in nano-Fe3O4@activated coke enhanced bio-system for coal pyrolysis wastewater treatment.

In current study, nano-Fe3O4@activated coke enhanced bio-system (FEBS) under limited-oxygen condition was applied for efficient treatment of aromatic organics in coal pyrolysis wastewater. Metagenomic analyses revealed functional microbiome linkages and mechanism involved in aromatic ring-cleavage. Based on biodegradation efficiency in different reactors, FEBS supplementation conferred the best organic removal (avg. 92.29%). It also showed a remarkable advantage in biodegradability maintenance (>40%) over control reactors. Metagenomics profiling revealed the degradation processes were driven by Fe3O4 redox reactions and microbial biofilm, while the suspended sludge was the principal force for aromatic mineralization. Based on the analysis of functional species and genes, most bacteria cleaved the benzene ring preferably through the aerobic pathways, mediated by catechol 1, 2-dioxygenase, catechol 2, 3-dioxygenase and protocatechuate 3, 4-dioxygenase (66-84%). Ecological network showed that Comamonas testosterone-centered microbiome and Azotobacter linked to the nitrogen (N)-heterocyclic ring-cleavage. Network linkage further demonstrated that Alicycliphilus and Acidovorax were the key tone taxa involved in benzene ring-cleavage. Finally, combined with analysis of degradation products, bacteria degraded N-heterocyclic ring containing organic aromatic compounds (quinoline) mainly through anaerobic processes, whereas cleavage of benzene ring preferred aerobic pathways. The enriched functional species were the primary reason for the enhanced biodegradation in FEBS.

Ecological and functional research into microbiomes for targeted phenolic removal in anoxic carbon-based fluidized bed reactor (CBFBR) treating coal pyrolysis wastewater (CPW).

Powdered activated carbon (PAC), lignite activated coke (LAC) and Fe-C carriers were applied to enhance CBFBRs to degrade targeted phenolics. In start-up stage, PAC and LAC equipped CBFBRs with higher environment adaptability and phenolic degradation capacity for phenol (>96%), p-cresol (>91%) and 3, 5-dimethylphenol (>84%) in comparison to Fe-C carrier. In recovery stage, the superior performance was also identified for CBFBRs in basis of PAC and LAC than Fe-C-based reactor. However, the Fe-C carrier assisted CBFBR with more stable degradation performance under impact loading. By comparing microbiomes, significantly enriched Brachymonas (54.80%-68.81%) in CBFBRs exerted primary role for phenolic degradation, and positively contributed to microbial network. Meanwhile, Geobacter in Fe-C-based reactor induced excellent impact resistance by enhancing interspecific electron transfer among microbes. Furthermore, the investigation on functional genes related to phenolic degradation revealed that anaerobic pathway accounted for demethylation procedure, while aerobic pathways dominated the phenolic ring-cleavage process.

Insights into electroactive biofilms for enhanced phenolic degradation of coal pyrolysis wastewater (CPW) by magnetic activated coke (MAC): Metagenomic analysis in attached biofilm and suspended sludge.

To investigate the role of electroactive biofilms for enhanced phenolic degradation, lignite activated coke (LAC) and MAC were used as carriers in moving-bed biofilm reactor (MBBR) for CPW treatment. In contrast to activated sludge (AS) reactor, the carriers improved degradation performance of MBBR. Although two MBBRs exerted similar degradation capacity with over 92% of COD and 93% phenols removal under the highest phenolics concentration (500 mg/L), the effluent of MAC-based MBBR remained higher biodegradability (BOD5/COD = 0.34 vs 0.18) than that of LAC-based MBBR. Metagenomic analysis revealed that electroactive biofilms determined phenolic degradation of MAC-based MBBR. Primarily, Geobacter (17.33%) started Fe redox cycle on biofilms and developed syntrophy with Syntrophorhabdus (6.47%), which fermented phenols into easily biodegradable substrates. Subsequently, Ignavibacterium (3.38% to 2.52%) and Acidovorax (0.46% to 8.83%) conducted biological electricity from electroactive biofilms to suspended sludge. They synergized with dominated genus in suspended sludge, Alicycliphilus (19.56%) that accounted for phenolic oxidation and nitrate reduction. Consequently, the significantly advantage of Geobater and Syntrophorhabdus was the keystone reason for superior biodegradability maintenance of MAC-based MBBR.

Selective adsorption and bioavailability relevance of the cyclic organics in anaerobic pretreated coal pyrolysis wastewater by lignite activated coke.

This study originally investigated the selective adsorption of cyclic organics in APCPW by LAC, corresponding to the change of the bioavailability. As a product from low rank coal, LAC showed more oxygen (O)-containing groups and mesoporous structure than PAC. Adsorption mechanisms were analyzed by equilibrium isotherms and kinetics models combined with physicochemical properties of adsorbent and adsorbates. The results indicated that selectivity of LAC was dominated by chemical interaction and its mesoporous, and was enhanced by hydrophobicity of adsorbates. In addition, PAC and LAC were applied for the treatment of APCPW. Compared with PAC, LAC adsorption exhibited superior removal efficiency of Tph, TOC and TN at 85.90%, 91.15% and 51.64%, respectively. Furthermore, preferential adsorption of biotoxic and bioresistant cyclic organics by LAC was further proved by GC-MS analysis, resulting in increased bioavailability of APCPW. Specifically, LAC exerted sustained detoxication capacity until 86.50% reduction of TU by D. magna evaluation, and lowered toxicity rank (TU = 4.51, classIII) to T. pyriformis than that after PAC adsorption (TU > 10, ClassIV). Meanwhile, biodegradability was also improved by 9.17% after LAC adsorption. Lastly, LAC would exhibit great economic benefits as an alternative for PAC in subsequent process after anaerobic pretreatment.

Synergistic degradation on phenolic compounds of coal pyrolysis wastewater (CPW) by lignite activated coke-active sludge (LAC-AS) process: Insights into succession of microbial community under selective pressure.

This study illustrated synergistic degradation of phenolic compounds by LAC-AS process via the insight into succession of microbial community under selective pressure. The results demonstrated that high phenols exhibited toxicity pressure to single AS process by eliminating non-tolerate bacteria, inducing vicious circulation by intermediates (catechol, nitrate, etc.) accumulation. However, LAC exerted another selective pressure and facilitated positive bio-community succession of moving biological bed reactor (MBBR). Firstly, it created rich microenvironments for diverse bacteria and promoted resilient adsorption for phenols with the assistance of biodegradation. Secondly, LAC enriched facultative bacteria, which developed multiple degradation paths on phenols and nitrogen based on multifunctional genes, counteracting the toxicity pressure. Specifically, phenols were degraded by the combination of anaerobic hydrolysis and oxidation, while conventional and shortcut nitrification-denitrification (SND) and nitrogen fixation all participated in nitrogen removal, achieving high removal of COD (93.49%), Tph (93.74%), TN (92.20%) and NH4+-N (93.20%) under the highest phenols.

Effect of low-intensity direct current electric field on microbial nitrate removal in coal pyrolysis wastewater with low COD to nitrogen ratio.

The coupling of bioelectrochemical system with the biological denitrification process (R1) was constructed for nitrate removal in coal pyrolysis wastewater (CPW) and the effect of low-intensity direct current electric field was investigated. Compared with control reactor (R2), the total nitrogen (TN) removal efficiency in R1 at the optimized voltage of 0.9 V was 94.20 ±â€¯2.14%, which was 14.42% higher than that in R2. The biofilm on the cathode of R1 enhanced the nitrate reducing, however, nitrite was only reduced by bacteria in suspended activated sludge, which was confirmed by cyclic voltammetry measurement (CV). Microbial community network analysis revealed that exoelectrogenic bacteria of Pseudomonas was enriched on the anode of R1, and the "small world", including Zoogloea, Pseudomonas and Arenimonas, was established under the stimulation of voltage. Therefore, Pseudomonas transferred electron to anode, and Arenimonas could utilize electron from anode to reduce nitrate, which enhanced TN removal in R1.

Enhanced nitrogen removal of coal pyrolysis wastewater with low COD to nitrogen ratio by partial nitrification-denitrification bioprocess assisted with polycaprolactone.

The purpose of this study is to investigate the enhancement of polycaprolactone (PCL) on total nitrogen (TN) removal of coal pyrolysis wastewater (CPW) with low COD to nitrogen ratio by partial nitrification-denitrification bioprocess (PNDB) in one single reactor. With the innovative combination of PCL and PNDB, the TN removal efficiency in the experimental reactor (signed as R1) was 10.21% higher than control reactor (R2). Nitrite accumulation percentage (NAP) in R1 was 82.02%, which was 17.49% higher than R2 at the dissolved oxygen (DO) concentration of 0.9-1.5 mg/L, for the reason that the extra DO was consumed by PCL biodegradation at the aerobic period. Gel permeation chromatography (GPC) results demonstrated that organics with the molecular weight of 185 Da, which could serve as additional carbon sources for denitrifiers, were generated during the PCL hydrolysis process at the anoxic period. PCL was hydrolyzed by extracellular enzymes with the break of the ester bond which was confirmed by FT-IR spectrometer. Microbial community analysis revealed that Ferruginibacter was the dominant hydrolysis bacteria in R1. Nitrosomonas were the main ammonium-oxidizing bacteria (AOB) and Hyphomicrobium were the denitrifiers in this study.

Comparative investigation on carbon-based moving bed biofilm reactor (MBBR) for synchronous removal of phenols and ammonia in treating coal pyrolysis wastewater at pilot-scale.

By regulating the extraction solvent and alkali in pretreatment, two carbon-based MBBRs were compared in pilot-scale to synchronously remove phenols and ammonia of coal pyrolysis wastewater (CPW) under fluctuant phenols-ammonia loadings. It revealed that lignite activated coke (LAC)-based MBBR performed more stable with phenols increasing (250-550 mg/L), and reached higher tolerance limit to ammonia (>320 mg/L) than activated carbon (AC)-based MBBR under fluctuant ammonia loadings. During the phenols-ammonia synchronous removal process, the LAC provided the firm basis for shock resistance due to superior resilient adsorption capacity, enhanced sludge property and microbial cooperation. Furthermore, microbial analysis revealed that the strengthened collaboration between archaea and facultative bacteria played the primary role in phenols-ammonia synchronous degradation. Specifically, the heterotrophic bacteria consumed phenols-ammonia by partial nitrification process and ammonia assimilation, following by denitrifying process to further eliminate phenols. The multifunctional Comamonas was the critical genus participating in all procedures.