Treatment of eutrophic water in pyrite-filled constructed wetland integrated with microelectrolysis driven by iron/sulfur cycle: Performance and mechanism.

This study developed a microelectrolysis-integrated constructed wetland with pyrite filler around the cathode (e-PCW) to treat eutrophic water. Results indicated that e-PCW effectively enhanced pyrite dissolution, converting solid-phase electron donors into bioavailable forms, thereby facilitating the enrichment of various denitrifying bacteria on pyrite surfaces. Importantly, iron-reducing and sulfur-reducing bacteria attached to the pyrite surfaces enhanced the conversion of ferric iron and sulfate, thereby driving iron and sulfur cycles and promoting electron transfer. Therefore, synergistic effects of pyrite and microelectrolysis made e-PCW achieve higher total nitrogen (TN) and total phosphorus (TP) removal efficiencies. With a hydraulic retention time of 24 h, the highest removal efficiencies of TN and TP achieved 78% and 75%, respectively. Furthermore, when eutrophic water containing high concentration of algae was fed into e-PCW, it consistently demonstrated superior TN and TP removal capabilities. This work provides a valuable approach to optimizing constructed wetland technology for treating eutrophic water.

Superior nitrate and chromium reduction synergistically driven by multiple electron donors: Performance and the related biochemical mechanism.

Nitrate and Cr(VI) are the typical and prevalent co-contaminants in the groundwater, how to synchronously and effectively diminish them has received growing attention. The most problem that currently limits the nitrate and Cr(VI) reduction technology for groundwater remediation is with emphasis on exploring the optimal electron donors. This study investigated the feasibility of utilizing the synergistical effect of inorganic electron donors (pyrite, sulfur) and inherently limited organics to promote synchronous nitrate and Cr(VI) removal, which meets the requirement of naturally low-carbon and eco-friendly technologies. The NO3--N and Cr(VI) removal efficiencies in the pyrite and sulfur involved mixotrophic biofilter (PS-BF: approximately 90.8 ± 0.6% and 99.1 ± 2.1%) were substantially higher than that in a volcanic rock supported biofilter (V-BF: about 49.6% ± 2.8% and 50.0% ± 9.3%), which was consistent with the spatial variations of their concentrations. Abiotic and biotic batch tests directly confirmed the decisive role of pyrite and sulfur for NO3--N and Cr(VI) removal via chemical and microbial pathways. A server decline in sulfate production correlated with decreasing COD consumption revealed that there was sulfur disproportionation induced by limited organics. Metagenomic analysis suggested that chemoautotrophic microbes like Sulfuritalea and Thiobacillus were key players responsible for sulfur oxidation, nitrate and Cr(VI) reduction. The metabolic pathway analysis suggested that genes encoding functional enzymes related to complete denitrification, S oxidation, and dissimilatory sulfate reduction were upregulated, however, genes encoding Cr(VI) reduction enzymes (e.g. chrA, chrR, nemA, and azoR) were downregulated in PS-BF, which further explained the synergistical effect of multiple electron donors. These findings provide insights into their potential cooperative interaction of multiple electron donors on greatly promoting nitrate and Cr(VI) removal and have implications for the remediation technology of nitrate and Cr(VI) co-contaminated groundwater.

Effect of Mn-HA on ARGs and MRGs in nitrogen-culturing sludge.

The simultaneous escalation in ARGs (antibiotic resistance genes) and MRGs (metal resistance genes) further complicates the intricate network of factors contributing to the proliferation of microbial resistance. Manganese, which has been reported to affect the resistance of bacteria to antibiotics and metals, plays a vital role in microbial nitrogen metabolism. Moreover, nitrifying and denitrifying populations are potential hosts for ARGs. In this study, manganese was introduced in its prevalent organic chelated form in the environment (Manganese humus chelates, Mn-HA) to a N metabolism sludge to explore the effect of manganese on MRGs and ARGs dissemination. Metagenomics results revealed that manganese availability enhances nitrogen metabolism, while a decrease in ARGs was noted which may be attributed to the inhibition of horizontal gene transfer (HGT), reflected in the reduced integrase -encoded gene int. Population analysis revealed that nitrifier and denitrifier genus harbor MRGs and ARGs, indicating that nitrifier and denitrifier are hosts of MRGs and ARGs. This raises the question of whether the prevalence of ARGs is always increased in metal-contained environments.

Biomineralized manganese oxide mediated nitrogen-contained wastewater treatment.

In recent years, manganese (Mn) has emerged as an accelerator for nitrogen metabolism. However, the bioactivity of manganese is limited by the restricted contact between microbes and manganese minerals in the solid phase and by the toxicity of manganese to microbes. To enhance the bioactivity of solid-phase manganese, biomineralized manganese oxide (MnOx) modified by Lactobacillus was introduced. Nitrogen removal performance have confirmed the effective role of biomineralized MnOx in accelerating the removal of total inorganic nitrogen (TIN). Metagenomic analysis has confirmed the enhancement of the nitrogen metabolic pathway and microbial extracellular electron transfer (MEET) in biomineralized MnOx treatment group (BIOA group). Additionally, the enrichment of manganese oxidation and denitrification genus indicates a coupling between nitrogen metabolism and manganese metabolism. One point of views is that biomineralized MnOx-mediated nitrogen transformation processes could serve as a substitute for traditional nitrogen removal processes.

Panoptic elucidation of algicidal mechanism of Raoultella sp. S1 against the Microcystis aeruginosa by TMT quantitative proteomics.

Harmful algal blooms (HABs) due to eutrophication are becoming a serious ecological disaster worldwide, threatening human health and the optimal balance of aquatic ecosystems. The traditional approaches to eradicate HABs yield several drawbacks in practical application, while microbial algicidal technology is garnering mounting recognition due to its high efficiency, eco-friendliness, and low cost. In our previous study, we isolated a bacterium strain Raoultella sp. S1 from eutrophic water with high efficiency of algicidal properties. This study further investigated the flocculation and inactivation efficiency of S1 on Microcystis aeruginosa at different eutrophic stages by customizing the algal cell densities. The supernatant extract of S1 strain exhibited remarkable flocculation and inactivation effects against low (1 × 106 cell/mL)and medium (2.7 × 106 cell/mL)concentrations of algal cells, but unexceptional for higher densities. The results further revealed that algal cells at low and medium counts manifested a more apparent antioxidant defense response, while the photosynthetic efficiency and relative electron transport rate were considerably reduced within 24 h. TEM observations confirmed the disruption of thylakoid membranes and cell structure of algal cells by algicidal substances. Moreover, TMT proteomics revealed alterations in protein metabolic pathways of algal cells during the flocculation and lysis stages at the molecular biological level. This signified that the disruption of the photosynthetic system is the core algicidal mechanism of S1 supernatant. In contrast, the photosynthetic metabolic pathways in the HABs were significantly upregulated, increasing the energy supply for the NADPH dehydrogenation process and the upregulation of ATPases in oxidative phosphorylation. Insufficient energy provided by NADPH resulted in a dwindled electron transport rate, stagnation of carbon fixation in dark reactions, and blockage of light energy conversion into chemical energy. Nonetheless, carbohydrate metabolism (gluconeogenesis and glycolysis) proteins were down-regulated and hampered DNA replication and repair. This study aided in unveiling the bacterial management of eutrophication by Raoultella sp. S1 and further arrayed the proteomic mechanism of algal apoptosis.

Differential Nitrous oxide emission and microbiota succession in constructed wetlands induced by nitrogen forms.

Nitrous oxide (N2O) emission during the sewage treatment process is a serious environmental issue that requires attention. However, the N2O emission in constructed wetlands (CWs) as affected by different nitrogen forms in influents remain largely unknown. This study investigated the N2O emission profiles driven by microorganisms in CWs when exposed to two typical nitrogen sources (NH4+-N or NO3--N) along with different carbon source supply (COD/N ratios: 3, 6, and 9). The results showed that CWs receiving NO3--N caused a slight increase in total nitrogen removal (by up to 11.8 %). This increase was accomplished by an enrichment of key bacteria groups, including denitrifiers, dissimilatory nitrate reducers, and assimilatory nitrate reducers, which enhanced the stability of microbial interaction. Additionally, it led to a greater abundance of denitrification genes (e.g., nirK, norB, norC, and nosZ) as inferred from the database. Consequently, this led to a gradual increase in N2O emission from 66.51 to 486.77 ug-N/(m2·h) as the COD/N ratio increased in CWs. Conversely, in CWs receiving NH4+-N, an increasing influent COD/N ratio had a negative impact on nitrogen biotransformation. This resulted in fluctuating trend of N2O emissions, which decreased initially, followed by an increase at later stage (with values of 122.87, 44.00, and 148.59 ug-N/(m2·h)). Furthermore, NH4+-N in the aquatic improved the nitrogen uptake by plants and promoted the production of more root exudates. As a result, it adjusted the nitrogen-transforming function, ultimately reducing N2O emissions in CWs. This study highlights the divergence in microbiota succession and nitrogen transformation in CWs induced by nitrogen form and COD/N ratio, contributing to a better understanding of the microbial mechanisms of N2O emission in CWs with NH4+-N or NO3--N at different COD/N ratios.

Magnetite-equipped algal-rich sediments for microbial fuel cells: Remediation of sediment organic matter pollution and mechanisms of remote electron transfer.

Using the bio-electrochemical methods for the restoration of high algae sediments is full of potential and challenges. How to promote extracellular electron transfer (EET) process in microbial fuel cells (MFC) is the key bottleneck. The study had explored the potential application of magnetite on accelerating electron transfer for improving the output of MFC and sediment pollution remediation. The results indicated that the organic matter degradation rate showed a remarkable increase of 27.45 %, and the voltage output was approximately 1.68 times higher compared to the MFC configured with regular sediment. Abundant electroactive bacteria (EABs), such as Geobacter and Burkholderiaceae, and fermentative bacteria were responsible for these results, accompanied by the enhanced fluorescence of humic substances (HS), increased concentration and activity of cytochrome C (25.05 % and 21.12 %), as well as elevated extracellular polymeric substance content. Moreover, the intrinsic EET mechanisms among Fe-oxides, HS, and EABs were explored. According to the electrochemical analysis and substance transformation, the EET process involved four stages: magnetite-enhanced direct electron transfer via strong conductivity, iron respiration mediating electron transfer to the electrode, the model quinone substance acting as an electron shuttle facilitating EET and iron reduction, and iron cycling mediating electron transfer. This study provides an effective strategy for pollution remediation in algal-rich sediment, which was beneficial for the harmless treatment and resource utilization of both algae and sediment, simultaneously.

Manganese oxide-loaded activated carbon for ammonium removal from wastewater: the roles of adsorption and oxidation.

The urgent need to address the severe issue of nitrogen pollution has prompted the search for a functional and easy recycling material. In this study, manganese oxides (MnOx) were loaded on activated carbon (AC), resulting in a composite known as AC-MnOx, for efficient ammonium removal from aqueous solutions. The results indicated a remarkable 15.6-fold increase in ammonium removal efficiency and a fivefold enhancement in removal capacity for AC-MnOx (3.20 mg/g) compared to AC. Under specific conditions (initial NH4+-N concentration of 15 mg/L, adsorbent dose of 2.5 g, pH of 6.5, and temperature of 35 ℃), the highest achieved ammonium removal efficiency reached 94.6%. Furthermore, the study distinguishes the contributions of catalytic oxidation and adsorption in the removal process. The adsorption process was effectively modeled using pseudo-second-order kinetics and Langmuir isotherm models. Interestingly, the amount of oxidation conversion (Ntur) exhibited a linear relationship with the dosage when the initial ammonium concentration was sufficiently high, while the relationship between initial ammonium concentration and the ratio of Ntur to adsorption capacity (Nsur) followed a negative exponential trend. The removal mechanisms involved electrostatic interaction between ammonium and the negatively charged dehydrogenated hydroxyl groups (- OHsur) or cation tunnel in crystal structures of MnOx, ion exchange adsorption, and the oxidation impact of MnOx. This research provides valuable insights into the application of immobilized MnOx media for ammonium removal. Moreover, filling AC-MnOx into constructed wetlands (CW) proved to be an effective method for reducing ammonium pollution, demonstrating its potential in the field of engineering wastewater treatment.

Mutual influence mechanism of nitrate and sulfamethoxazole on their biotransformation in poly (3-hydroxybutyrate-3-hydroxyvalerate) supported denitrification biofilter for a long-term operation.

Nitrate and SMX both play a critical role in their biotransformation in biodegradable polymer-supported denitrification biofilters. However, the mutual influences of nitrate and SMX on their biotransformation for long-term operation remained obscure. Results showed SMX and nitrate had divergent effects on SMX removal. SMX removal rates was positively related with its loading rates, whereas they were negatively related to NLRs. The most abundant metabolite C10H14O3N3S (the reduced form of SMX moiety) from the N-O bond cleavage pathway by UHPLC-LTQ-Orbitrap-MS/MS and effluent TOC variations confirmed the presence of electron donor competition between nitrate and SMX. SMX less than 1000 µg/L had a negligible influence on denitrification performance. Denitrifiers such as Azospira and Denitratisoma were still enriched after chronic exposure, and nosZ/narG positively correlated with sul1/sul2 resistance genes, which were both responsible for the negligible influence of SMX. This work could guide the operational management of denitrification biofilters for simultaneous nitrate and antibiotics removal.

Microbiota and genetic potential for reducing nitrous oxide emissions by biochar in constructed wetlands.

The denitrification process in constructed wetlands (CWs) is responsible for most of the nitrous oxide (N2O) emissions, which is an undesired impact on the ecology of sewage treatment systems. This study compared three types of CWs filled with gravel (CW-B), gravel mixed with natural pyrite (CW-BF), or biochar (CW-BC) to investigate their impact on microbiota and genetic potential for N2O generation during denitrification under varying chemical oxygen demand (COD) to nitrate (NO3--N) ratios. The results showed that natural pyrite and biochar were superior in enhancing COD (90.6-91.2 %) and NO3--N removal (90.0-93.5 %) in CWs with a COD/NO3--N ratio of 9. The accumulation of NO2--N during the denitrification process was the primary cause of N2O emission, with the fluxes ranging from 95.6-472.0 µg/(m2·h) in CW-B, 92.9-400 µg/(m2·h) in CW-BF, and 54.0-293.3 µg/(m2·h) in CW-BC. The addition of biochar significantly reduced N2O emissions during denitrification, while natural pyrite had a lesser inhibitory effect on N2O emissions. The three types of substrates also influenced the structure of microbiota in the biofilm, with natural pyrite enriched nitrogen transformation microorganisms, especially for denitrifiers. Notably, biochar significantly enhanced the abundance of nosZ and the ratio of nosZ/(norB + norC), which are critical factors in reducing N2O emissions from CWs. Overall, the results suggest that the biochar-induced changes in microbiota and genetic potential during denitrification play a significant role in preventing N2O production in CWs, especially when treating sewage with a relatively high COD/NO3--N ratio.

A photocatalytic-microbial coupling system for simultaneous removal of harmful algae and enhanced denitrification: Construction, performance and mechanism of action.

Recently, harmful algal blooms (HABs) have become occurred with increasingly frequency worldwide. High nitrate content is one of the primary causes of eutrophication. Research has shown that photocatalytic materials enhance the effectiveness of microbial denitrification while removing other contaminants, despite some shortcomings. Based on this, we loaded TiO2/C3N4 heterojunctions onto weaveable, flexible carbon fibers and established a novel photocatalytically enhanced microbial denitrification system for the simultaneous removal of harmful algae and Microcystin-LR. We found that 99.35% of Microcystis aeruginosa and 95.34% of MC-LR were simultaneously and effectively removed. Compared to existing denitrification systems, the nitrate removal capacity improved by 72.33%. The denitrifying enzyme activity and electron transport system activity of microorganisms were enhanced by 3.54-3.86 times. Furthermore, the microbial community structure was optimized by the regulation of photogenerated electrons, and the relative abundance of main denitrifying bacteria increased from 50.72% to 66.45%, including Proteobacteria and Bacteroidetes. More importantly, we found that the increased secretion of extracellular polymeric substances by microorganisms may be responsible for the persistence of the reinforcing effect caused by photogenerated electrons in darkness. The higher removal of Microcystis aeruginosa and Microcystin-LR (MC-LR) achieved by the proposed system would reduce the frequency of HAB outbreaks and prevent the associated secondary pollution.

The evolution of nitrogen transformation microorganism consortium under continued manganese domestication conditions.

Manganese redox-stimulated bioremediation of nitrogen wastewater is receiving increasing attention. However, the nitrogen metabolic capacity and community evolution during manganese-mediated nitrogen transformation process under continued manganese domestication conditions are ambiguous. In this study, nitrogen- metabolizing microbial consortiums were incubated with synthesized Mn-humic acid complex (Mn-HA) for one month (M1), three months (M2) and six months (M3), respectively. During the Mn-HA incubation period, Bio-MnOx accompanying with bacterial consortiums (MnOB consortiums) with high TIN removal capacities were obtained. The TIN removal rates in M1, M2 and M3 were 0.220, 1.246 and 4.237 mg·L-1·h-1, respectively, which were 15.961, 90.006 and 1550.006 times higher than CK (Control Check group, no Mn-HA added group) (0.014 mg·L-1·h-1), respectively. Functional genes (amoA, AMX and narG) were most abundant in M3, which was associated with the highest nitrogen removal rate in M3. MnOB1 (bacterial consortium in M1), including Geobactor, Geothrix, Anaeromyxobacter and Bacillus, may be responsible for the Mnammox-NDMO (MnOx reduction coupled to ammonium oxidation - nitrate/nitrite-dependent low-valent Mn oxidation) process. MnOB3 (bacterial consortium in M2) enriched nitrifying bacteria Ellin6067, and denitrifying bacteria Denitratisoma, which dominated nitrogen transformation. MnOB6 (bacterial consortium in M3) enriched denitrifiers Denitratisoma, nitrifiers Ellin6067 and potential anammox bacteria SM1A02, Candidatus_Brocadia. Combined with the reduced abundance of Nitrospirae, a short-cut partial nitrification and denitrification (PND) or partial nitrification, denitrification and anammox (PNDA) could occurred in M2 and M3. It is suggested that community may have evolved into an energetically efficient short-cut nitrification, denitrification and anammox consortium to replace the full-range nitrification and denitrification community in M1 and CK under the continued manganese domestication conditions. Enhanced metabolic pathways of hydroxylamine oxidation and the nitric oxide reduction may confirm that PND or PNDA occurred in M2 and M3.

Manganese-mediated ammonium removal by a bacterial consortium from wastewater: Experimental proof and biochemical mechanisms.

Manganese-redox-mediated nitrogen transformation is promising for ammonium wastewater treatment. However, due to the limited contact between insoluble Mn and the microbe, extracellular electron transfer (EET) inefficiencies become a technical bottleneck in the technical practical application. To overcome this obstacle, humic acid (HA) was introduced to synthesize manganese-humic acid complex (Mn-HA) to increase Mn solubility. The TIN (Total Inorganic Nitrogen) removal rate constant k was 3.18, 1.08, 3.56, 1.13 and 1.05 times higher than CK (Control group) at 10, 15, 20, 40 and 60 mg/L influent nitrate in the MH group, respectively. Mn-HA was inferred to stimulated the nitrogen removal by providing more reaction active sites, bridging Mn-O bonds to transfer electrons and playing a redox role in the respiratory chain. A Mnammox-NDMO (manganese oxide reduction-coupled ammonium oxidation - nitrate/nitrite- dependent manganese oxidation) bacteria consortium was enriched in MH group, containing Mnammox bacteria Geothrix, Geobacter and NDMO bacteria Pseudomonas and Bacillus.

Microelectrolysis-integrated constructed wetland with sponge iron filler to simultaneously enhance nitrogen and phosphorus removal.

Integrating sponge iron (SI) and microelectrolysis individually into constructed wetlands (CWs) to enhance nitrogen and phosphorus removal are challenged by ammonia (NH4+-N) accumulation and limited total phosphorus (TP) removal efficiency, respectively. In this study, a microelectrolysis-assisted CW using SI as filler surrounding the cathode (e-SICW) was successfully established. Results indicated that e-SICW reduced NH4+-N accumulation and intensified nitrate (NO3--N), the total nitrogen (TN) and TP removal. The concentration of NH4+-N in the effluent from e-SICW was lower than that from SICW in the whole process with 39.2-53.2 % decrease, and as the influent NO3--N concentration of 15 mg/L and COD/N ratio of 3, the removal efficiencies of NO3--N, TN and TP in e-SICW achieved 95.7 ± 1.9 %, 79.8 ± 2.5 % and 98.0 ± 1.3 %, respectively. Microbial community analysis revealed that hydrogen autotrophic denitrifying bacteria of Hydrogenophaga was highly enriched in e-SICW.

Analysis of a novel strain Brevundimonas KX-1 capable of degrading 3-chlorocarbazole based on the whole genome sequence.

In this study, a strain was isolated from a sewage treatment plant in Jiangsu Province, China. The strain was identified as Brevundimonas sp. KX-1. After 5 days, 50.2% 3-chlorocarbazole (3-CCZ) was degraded under the optimum condition as follows: 1 g/L starch, 30 °C, pH 6.5 and 50 mg/L 3-CCZ. The degradation of 3-CCZ by KX-1 conformed to the first-order kinetic model under different initial concentrations in this experiment. The intermediate product of 3-CCZ degradation was identified as (2E,4Z)-6-(2-amino-5-chlorophenyl)-2-hydroxy-6-oxohexa-2,4-dienoic acid. The activities of the meta-cleavage enzymes for biphenyl-2,3-diol (the analogs of intermediate product 2'-amino-5'-chloro-[1,1'-biphenyl]-2,3-diol) were measured with the crude extracts of cells grown in the presence of 3-CCZ. The complete genome of KX-1 was sequenced and compared with the Brevundimonas diminuta BZC3. BZC3 and KX-1 belonged to the same species, displaying the genetic similarity of 99%. But BZC3 could efficiently degrade gentamicin for the potential microbial function analysis. Compared with BZC3, KX-1 possessed the primary function annotations about transportation and metabolism of amino acids (6.65%) and the transportation and metabolism of carbohydrates (5.96%). In addition, KX-1 was rich in sucrose and starch metabolism pathways (ko00500) compared with the genome of BZC3, indicating the high efficiency of KX-1 for starch utilization during degradation. This article reveals the difference between strain KX-1 and bacteria of the same genus in terms of the whole genome sequence, demonstrating that KX-1 is a novel strain Brevundimonas with the ability to degrade 3-CCZ.

Toxicity of ionic liquids against earthworms (Eisenia fetida).

Ionic liquids (ILs) are widely used in frontier fields because of their highly tunable properties. Although ILs may have adverse effects on organisms, few studies have focused on their effect on earthworm gene expression. Herein we investigated the toxicity mechanism of different ILs towards Eisenia fetida using transcriptomics. Earthworms were exposed to soil containing different concentrations and types of ILs, and behavior, weight, enzymatic activity and transcriptome were analyzed. Earthworms exhibited avoidance behavior towards ILs and growth was inhibited. ILs also affected antioxidant and detoxifying enzymatic activity. These effects were concentration and alkyl chain length-dependent. Analysis of intrasample expression levels and differences in transcriptome expression levels showed good parallelism within groups and large differences between groups. Based on functional classification analysis, we speculate that toxicity mainly occurs through translation and modification of proteins and intracellular transport functions, which affect protein-related binding functions and catalytic activity. KEGG pathway analysis revealed that ILs may damage the digestive system of earthworms, among other possible pathological effects. Transcriptome analysis reveals mechanisms that cannot be observed by conventional toxicity endpoints. This is useful to evaluate the potential environmental adverse effects of the industrial use of ILs.

Efficient removal of 3,6-dichlorocarbazole with Fe0-activated peroxymonosulfate: performance, intermediates and mechanism.

Nowadays, polyhalogenated carbazoles (PHCZs) are a major pollutant that has recently sparked widespread concern. In this work, peroxymonosulfate (PMS) was activated by zero valent iron (Fe0) to remove 3,6-dichlorocarbazole (3,6-CCZ). First, the key parameters influencing 3,6-CCZ degradation (PMS dosage, Fe0 dosage, initial pH, temperature and co-existing ions) were determined. Under the determined optimum conditions, the removal rate of 3,6-CCZ reached 100% within 1.5 h. Sulfate radicals (SO4·-), hydroxyl radicals (OH·), and singlet oxygen (1O2) generated in the reaction were directly identified with 0.1 M 5,5-dimethyl-1-pyrrolidine N-oxide (DMPO) by in-situ electron paramagnetic resonance (EPR) and indirectly identified by radical quenching experiments. The main reactive oxygen species (ROS) were different from most reported hydroxyl radicals (OH·) and sulfate radicals (SO4·-). In this study, it was found that OH· and 1O2 play a major role. Then, fresh and reacted Fe0 were characterized by XRD, SEM, and XPS. Iron corrosion products such as Fe2O3, Fe3O4, and FeOOH were generated. Finally, 3,6-CCZ degradation intermediates were identified by GC-MS and its degradation pathway was speculated. The intermediate pathway confirmed the combined action of (OH·) and (1O2) in 3,6-CCZ removal. This study provides new insight into the activation mechanism of Fe0-activated PMS and the removal mechanism of 3,6-CCZ.Highlights Fe0 is a long-lasting and efficient catalyst of PMS for the degradation of 3,6-CCZ.The key parameters influencing 3,6-CCZ degradation were determined.The degradation pathways of 3,6-CCZ were inferred.OH· and 1O2 were the main ROS in Fe0-activated PMS system.

Reducing the inhibitive effect of fluorine and heavy metals on nitrate reduction by hydroxyapatite substrate in constructed wetlands.

Bio-toxic inorganic pollutants, e.g., fluorine (F) and heavy metals (HMs), in wastewaters are the potential threats to nitrate (NO3--N) reduction by microorganisms in constructed wetlands (CWs). Selection of suitable substrate with high F and HMs adsorption efficiency and capacity is a potential alternative for simultaneous removal of these pollutants in CWs. Herein, this study investigated the feasibility of applying hydroxyapatite (HA)-gravel media for F and HMs adsorption and its effect on NO3--N reduction in CWs (HA CWs) by comparing the CWs filled with gravel substrate (CK CWs). The results indicated that the removal efficiency of F, Cr, As, and NO3--N in HA CWs increased by 113.6-, 3.3-, 2.7-, and 0.6-folds, respectively, compared to CK CWs. The NO3--N reduction rate decreased by 11-46% in CK CWs after the presence of F and HMs in influent, while for HA CWs, it was only 13-22%. Excellent F and HMs adsorption capacity of HA substrate availed for wetland plants resisting F/HMs toxicity and making catalase activity lower. The HA substrate in CWs resulted in the certain succession of nitrogen-transforming bacteria, e.g., nitrifiers (Nitrospira) and denitrifiers (Thiobacillus and Desulfobacterium). More importantly, key functional genes, including nirK/nirS, korA/korB, ChrA/ChrD, arsA/arsB, catalyzing the processes of nitrogen biotransformation, energy metabolism, NO3--N and metal ions reduction were also enriched in HA CWs. This study highlights HA substrate reduce the inhibitive effect of F and HMs on NO3--N reduction, and provides new insights into how microbiota structurally and functionally respond to different substrates in CWs.

Study on the management efficiency of lanthanum/iron co-modified attapulgite on sediment phosphorus load.

Attapulgite co-modified by lanthanum-iron (MT-LHMT) was used to study its effectiveness and mechanism in controlling phosphorus release from sediments. MT-LHMT has high adsorption capacity for phosphate and the maximum adsorption capacity of MT-LHMT to phosphate can reach 75.79 mg/g. The mechanism mainly involved electrostatic action, surface precipitation and ligand exchange between MT-LHMT bonded hydroxyl and phosphate to form La-O-P and Fe-O-P inner-sphere complexes. MT-LHMT has excellent adsorption performance in the pH range of 3-8. In addition to HCO3-, CO32- and HA- had a negative effect on the phosphorus removal of MT-LHMT, while NO3-, Cl-, SO42-, K+, Ca2+ and Mg2+ had a positive or no effect on phosphorus removal. MT-LHMT significantly reduced the risk of phosphorus release from overlying water in different dose effects and covering methods, as well as the unstable inactivation of flowing phosphorus, sediment dissolved reactive phosphorus (DRP) and available phosphorus with medium diffusion gradient in thin film in the sediment-water interface (Labile-PDGT). The MT-LHMT capping wrapped with fabric can reduce the risk of nitrogen release from sediment to overlying water more than only MT-LHMT capping. The results of this study showed that the MT-LHMT capping wrapped with fabric has high potential and can be used as an active capping material to manage the nitrogen and phosphorus load in surface water.

Simultaneous nitrification and denitrification in a PCL-supported constructed wetland with limited aeration.

Considerable advances have been made in the substrate design and operation strategies of constructed wetlands to facilitate nitrogen elimination. However, few studies examined the complicated interaction between solid organic substrates and limited aeration on nitrogen removal. A vertical flow constructed wetlands in gradient distribution of inorganic and solid organic substrates (polycaprolactone/PCL) (P-VFCW) and a controlled vertical flow constructed wetland without PCL (C-VFCW) were developed for the tertiary treatment of municipal tailwater. Results indicated that ammonia was nearly converted to nitrate, while the total nitrogen removal efficiencies (TNREs) in C-VFCW were negligible. In P-VFCW, however, optimal TNREs approached 95% with an aeration rate of 0.06 mL·min-1 and hydraulic retention time (HRT) of 24 h, and simultaneous nitrification and denitrification process (SND) in aerobic conditions was confirmed. As for the spatial microbial community structure evolution, Comamonas, which is associated with heterotrophic nitrification and anoxic/aerobic denitrification, was enriched along the vertical profiles of P-VFCW. Autotrophic nitrifier (Nitrospira), aerobic denitrifier (Bradyrhizobium and Azospira), and anoxic denitrifier (Ignavibacterium and Methyloversatilis) were dominated in different depths of P-VFCW, respectively. Besides, Canna indica biomass in P-VFCW was significantly larger than that in C-VFCW, which was attributed to the plant adaption response to diverse nitrogen. The P-VFCW in gradient distribution of inorganic and solid carbon sources under limited aeration is a promising technology for advanced nitrogen removal.