Efficient photocatalytic reduction of nitrate byproducts during anammox process by novel extracellular polymeric substances-embedded NH2-MIL-101(Fe) photocatalysts.

Anaerobic ammonium oxidation (anammox) is an efficient nitrogen removal process; however, nitrate byproducts hampered its development. In this study, extracellular polymeric substances (EPS) were embedded into NH2-MIL-101(Fe), creating NH2-MIL-101(Fe)@EPS to reduce nitrate. Results revealed that chemical nitrate reduction efficiency of NH2-MIL-101(Fe)@EPS surpassed that of NH2-MIL-101(Fe) by 17.3 %. After adding 0.5 g/L NH2-MIL-101(Fe)@EPS within the anammox process, nitrate removal efficiency reached63.9 %, consequently elevating the total nitrogen removal efficiency to 92.4 %. 16S rRNA sequencing results elucidated the predominant role of Candidatus Brocadia within NH2-MIL-101(Fe)@EPS-anammox system. Concurrently, sufficient photogenerated electrons were transferred to microorganisms, promoting the growth of Desnitratisoma and OLB17. Additionally, photogenerated electrons activated flavin and Complex III, thereby up-regulating crucial genes involved in intra/extracellular electron transfer. Subsequently, denitrification and dissimilatory nitrate reduction to ammonium were activated to reduce nitrate. In summary, this study achieved a notable rate of photocatalytic nitrate reduction within anammox process through the NH2-MIL-101(Fe)@EPS photocatalysts.

Mechanism of gel immobilization driving efficient anammox in mainstream partial nitritation/anammox process: Structural characterization and multi-perspective microbial analysis.

Here, the mechanism of encapsulated anammox bacteria (AnAOB) driving efficient nitrogen removal in the mainstream partial nitritation/anammox process is revealed. The results show that a high nitrogen removal rate (1.21±0.02 kgN·(m3·d)-1) was achieved due to the abundant micropore structure inside the anammox immobilized filler, ensuring good connectivity, and a stable aggregation capacity, reducing dependence on extracellular polymeric substances. AnAOB were uniformly distributed throughout all regions of the immobilized filler, and their abundance was higher than that of the control anammox granular sludge (AnGS). Conversely, cracks appeared on the surface of the AnGS, and hollows formed inside. The metagenome analysis revealed that the immobilized filler supported the coexistence of multiple AnAOB, and the appropriate niche enhanced coordination between the AnAOB and dominant companion microorganisms. In contrast, AnGS exhibited stronger NH4+-N and NO2--N loops, potentially reducing the total nitrogen removal efficiency. This study promotes the mainstream application of anammox.

Simultaneous inorganic nitrogen and phosphate removal by aerobic-heterotrophic fungus Fusarium keratoplasticum FSP1: Performance, pathway and application.

Fungi with multiple contaminant removal function have rarely been studied. Here, a novel fungal strain Fusarium keratoplasticum FSP1, which was isolated from halophilic granular sludge, is reported for first time to perform simultaneous nitrogen and phosphate removal. The strain showed wide adaptability under C/N ratios of 30-35, salinities of 0 %-3 % (m/v), and pH of 7.5-9.5. The maximum removal rates of ammonium, nitrate and nitrite were 4.43, 4.01 and 2.97 mg N/L/h. The nitrogen balance, enzyme activity and substrate conversion experiments demonstrated a single strain FSP1 can assimilate inorganic nitrogen and convert inorganic nitrogen to gaseous nitrogen through heterotrophic nitrification or aerobic denitrification. About 39 %-42 % of the degraded phosphorus was in the extracellular polymeric substances (EPS). Orthophosphate was the main phosphorus species in the cell, whereas phosphate monoester and diester were in the EPS. The novel strain FSP1 is a potential candidate for wastewater treatment.

Non-rhizosphere reinforces the contributions of Feammox and anammox to nitrogen loss than rhizosphere in riparian zones.

The emergence of anaerobic ammonium oxidation (anammox) coupled to iron reduction (named Feammox) refreshes the microbial pathways for nitrogen (N) loss. However, the ecological role of Feammox, compared with conventional denitrification and anammox, in microbial N attenuation in ecosystems remains unclear. Here, the specific contribution of Feammox to N loss and the underlying microbiome interactive characteristics in a riparian ecosystem were investigated through 15N isotope tracing and molecular analysis. Feammox was highlighted in the riparian interface soils and maximally contributed 14.2% of N loss. Denitrification remained the dominant contributor to N loss (68.0%-95.3%), followed by anammox (5.7%-19.1%) and Feammox (0-14.2%). The rates of Feammox and anammox significantly decreased in rhizosphere soils (0.15 ± 0.08 µg N g-1 d -1 for Feammox, 0.80 ± 0.39 µg N g-1 d -1 for anammox) compared with those in non-rhizosphere soils; however, the activities of denitrification remarkably increased in the rhizosphere (13.17 ± 3.71 µg N g-1 d -1). In rhizosphere soils, the competition between bioavailable organic matter (e.g., amino acids and carbohydrates) and ammonium for electron acceptor [i.e., Fe(III)] was the vital inducement for restricted Feammox, while the nitrite consumption boosted by heterotrophic denitrifiers was responsible for weakened anammox. The functional gene of autotrophic Acidimicrobiaceae bacterium A6, instead of heterotrophic Geobacteraceae spp., was significantly positively correlated with Feammox activity. Rare iron-reducing bacteria showed higher node degrees in the non-rhizosphere network than in the rhizosphere network. A syntrophic relationship was found between iron-reducing bacteria (e.g., Anaeromyxobacter, Geobacter) and iron-oxidizing bacteria (e.g., Sideroxydans) in the non-rhizosphere network and facilitated the Feammox pathway. This study provides an in-depth exploration of microbial driven N loss in a riparian ecosystem and introduces new insights into riparian management practices toward high-efficient N pollution alleviation.

Long-term effect of light rare earth element neodymium on Anammox process.

During the mining of rare earth minerals, the application of neodymium-containing manures, and the treatment of spent neodymium iron boron magnet, the generation of ammonia wastewater containing neodymium is increasing. Thus, the effects of neodymium (Nd(III)) on anaerobic ammonium oxidation (Anammox) were investigated from the aspects of performance, kinetics, statistics, microbial community and sludge morphology, and the recovery strategy of EDTA-2Na wash was discussed. The nitrogen removal efficiency of the Anammox reactor decreased significantly and eventually collapsed at the Nd(III) dosing levels of 20 and 40 mg L-1, respectively. And the toxicity of Nd(III) to AnAOB was determined by the amount internalized into the cells. The EDTA-2Na wash successfully increased the total nitrogen removal rate (TNRR) of Nd(III)-inhibited Anammox to 41.60% of its initial value within 30 days, and the modified Boltzmann model accurately simulated this recovery process. The transient and extended effects of Nd(III), self-recovery, and EDTA-2Na wash on Anammox were effectively assessed using a one-sample t-test. 16S rRNA gene sequencing indicated that Nd(III) remarkably decreased the relative abundance of Planctomycetes and Candidatus Brocadia. The scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) revealed crystal-like neodymium particles on the surface of Anammox sludge. The above-mentioned results demonstrate that the concentration of Nd(III) should be below the toxicity threshold (20 mg L-1) when treating ammonia wastewater containing neodymium by Anammox, and also emphasize the importance of an appropriate recovery strategy.

The biochar/Fe-modified biocarrier driven simultaneous NDFO and Feammox to remove nitrogen from eutrophic water.

Novelty techniques of Fe(III) reduction coupled to anaerobic ammonium oxidation (i.e. Feammox) and nitrate-dependent Fe(II) oxidation (i.e. NDFO) provide new insights into autotrophic nitrogen removal from eutrophic waters. Given that Feammox and NDFO can theoretically complete the simultaneous NH+ 4-N and NO- 3-N removal via Fe(III)/Fe(II) cycle, this study introduces iron powder to the surface of the biocarrier as a solid-phase source of Fe, and biochar was used as an electron shuttle to mix with the iron powder to improve the bioavailability of iron. Batch experiments was carried out for 70 days using simulated eutrophic water as the medium to investigate the effects of the modified biocarrier for enhanced nitrogen removal. The results showed that BC1 (Fe:BC=1:1) with the highest relative Fe content exhibited the highest nitrogen removal efficiency of 66.74%. XPS and XRD results showed both Fe(III) and Fe(II) compounds on the biocarrier surface, confirming the occurrence of Fe(III)/Fe(II) cycle. The ex-situ activity test indicated that functional activity was positively correlated with the iron content of the biocarrier. The in-situ experiments with different substrates showed the occurrence of Feammox and NDFO. NDFO bacteria (Gallionellaceae), Feammox bacteria (Alicycliphilus), denitrifying and digesting bacteria were enriched, suggesting that the coupled nitrogen removal of NDFO and Feammox is the result of cooperation between different functional microorganisms. Thus, the Fe-modified biocarrier showed superior performance and application potential in catalyzing autotrophic nitrogen removal from eutrophic water by functional microorganisms.

Enhancement of Ammonium Oxidation at Microoxic Bioanodes.

Bioelectrochemical systems (BESs) are considered to be energy-efficient to convert ammonium, which is present in wastewater. The application of BESs as a technology to treat wastewater on an industrial scale is hindered by the slow removal rate and lack of understanding of the underlying ammonium conversion pathways. This study shows ammonium oxidation rates up to 228 ± 0.4 g-N m-3 d-1 under microoxic conditions (dissolved oxygen at 0.02-0.2 mg-O2/L), which is a significant improvement compared to anoxic conditions (120 ± 21 g-N m-3 d-1). We found that this enhancement was related to the formation of hydroxylamine (NH2OH), which is rate limiting in ammonium oxidation by ammonia-oxidizing microorganisms. NH2OH was intermediate in both the absence and presence of oxygen. The dominant end-product of ammonium oxidation was dinitrogen gas, with about 75% conversion efficiency in the presence of a microoxic level of dissolved oxygen and 100% conversion efficiency in the absence of oxygen. This work elucidates the dominant pathways under microoxic and anoxic conditions which is a step toward the application of BESs for ammonium removal in wastewater treatment.

Simple and Low-Cost Electroactive Membranes for Ammonia Recovery.

Ammonia is considered a contaminant to be removed from wastewater. However, ammonia is a valuable commodity chemical used as the primary feedstock for fertilizer manufacturing. Here we describe a simple and low-cost ammonia gas stripping membrane capable of recovering ammonia from wastewater. The material is composed of an electrically conducting porous carbon cloth coupled to a porous hydrophobic polypropylene support, that together form an electrically conductive membrane (ECM). When a cathodic potential is applied to the ECM surface, hydroxide ions are produced at the water-ECM interface, which transforms ammonium ions into higher-volatility ammonia that is stripped across the hydrophobic membrane material using an acid-stripping solution. The simple structure, low cost, and easy fabrication process make the ECM an attractive material for ammonia recovery from dilute aqueous streams, such as wastewater. When paired with an anode and immersed into a reactor containing synthetic wastewater (with an acid-stripping solution providing the driving force for ammonia transport), the ECM achieved an ammonia flux of 141.3 ± 14.0 g.cm-2.day-1 at a current density of 6.25 mA.cm-2 (69.2 ± 5.3 kg(NH3-N)/kWh). It was found that the ammonia flux was sensitive to the current density and acid circulation rate.

Rh(II)/Pd(0) Dual Catalysis: Interception of Ammonium Ylide with Allyl Palladium to Construct 2,2-Disubstituted Tetrahydroquinoline Derivatives.

New synthetic methods to construct 2,2-disubstituted tetrahydroquinoline derivatives are of significant value in pharmaceutical chemistry. Herein, a Rh(II)/Pd(0) dual-catalyzed diazo α-aminoallylation reaction has been developed between allylpalladium(II) and ammonium ylides derived from the Rh2(OAc)4-mediated intramolecular N-H bond insertion reaction of diazo compounds, affording various 2,2-disubstituted tetrahydroquinoline derivatives in good yields up to 93% with high chemoselectivities under mild reaction conditions. A substrate scope investigation reveals broad ester substituent tolerance, and control experiments provide the basis for a proposed reaction mechanism.

Microbial ecological responses of partial nitritation/anammox granular sludge to real water matrices and its potential application.

Granular sludges are commonly microbial aggregates used to apply partial nitritation/anammox (PN/A) processes during efficient biological nitrogen removal from ammonium-rich wastewater. Considering keystone taxa of anammox bacteria (AnAOB) in granules and their sensitivity to unfavorable environments, it is essential to investigate microbial responses of autotrophic PN/A granules to real water matrices containing organic and inorganic pollutants. In this study, tap water, surface water, and biotreated wastewater effluents were fed into a series of continuous PN/A granular reactors, respectively, and the differentiation in functional activity, sludge morphology, microbial community structure, and nitrogen metabolic pathways was analyzed by integrating kinetic batch testing, size characterization, and metagenomic sequencing. The results showed that feeding of biotreated wastewater effluents causes significant decreases in nitrogen removal activity and washout of AnAOB (dominated by Candidatus Kuenenia) from autotrophic PN/A granules due to the accumulation of heavy metals and formation of cavities. Microbial co-occurrence networks and nitrogen cycle-related genes provided evidence for the high dependence of symbiotic heterotrophs (such as Proteobacteria, Chloroflexi, and Bacteroidetes) on anammox metabolism. The enhancement of Nitrosomonas nitritation in the granules would be considered as an important contributor to greenhouse gas (N2O) emissions from real water matrices. In a novel view on the application of microbial responses, we suggest a bioassay of PN/A granules by size characterization of red-color cores in ecological risk assessment of water environments.

Meta-omics profiling of full-scale groundwater rapid sand filters explains stratification of iron, ammonium and manganese removals.

Rapid sand filters (RSF) are an established and widely applied technology for groundwater treatment. Yet, the underlying interwoven biological and physical-chemical reactions controlling the sequential removal of iron, ammonia and manganese remain poorly understood. To resolve the contribution and interactions between the individual reactions, we studied two full-scale drinking water treatment plant configurations, namely (i) one dual-media (anthracite and quartz sand) filter and (ii) two single-media (quartz sand) filters in series. In situ and ex situ activity tests were combined with mineral coating characterization and metagenome-guided metaproteomics along the depth of each filter. Both plants exhibited comparable performances and process compartmentalization, with most of ammonium and manganese removal occurring only after complete iron depletion. The homogeneity of the media coating and genome-based microbial composition within each compartment highlighted the effect of backwashing, namely the complete vertical mixing of the filter media. In stark contrast to this homogeneity, the removal of the contaminants was strongly stratified within each compartment, and decreased along the filter height. This apparent and longstanding conflict was resolved by quantifying the expressed proteome at different filter heights, revealing a consistent stratification of proteins catalysing ammonia oxidation and protein-based relative abundances of nitrifying genera (up to 2 orders of magnitude difference between top and bottom samples). This implies that microorganisms adapt their protein pool to the available nutrient load at a faster rate than the backwash mixing frequency. Ultimately, these results show the unique and complementary potential of metaproteomics to understand metabolic adaptations and interactions in highly dynamic ecosystems.

Reactive and microbial inhibitory mechanisms depicting the panoramic view of pH stress effect on common biological nitrification.

pH is a crucial factor of microbial nitrification, which often combines with high-strength ammonium to influence nitrogen removal pathway in wastewater treatment. However, the detailed inhibitory mechanisms of pH stress are not sufficiently disclosed yet. In this study, the pH stress effect on nitrification was comprehensively studied by a set of experiments which identified the reactivity of nitrification processes and activity of nitrifiers, the time dependence of inhibition effect and the hybrid pH stress effect with ammonium. The results revealed two distinct inhibitory mechanisms dominating in alkaline and acid ranges. In alkaline range (pH > 8), pH stress causes physiological damages on microorganisms which is named as microbial inhibition. It has the features of less recoverability of nitrifiers, time-dependent inhibition effect and low pH-tolerance of nitrite oxidation bacteria. Free ammonia enhanced microbial inhibition and greatly promoted nitrite accumulation. A novel reactive inhibition mechanism dominated in acid range (pH < 7) was disclosed. It only impedes ammonia oxidation process (AOP) but not impair microbial activity obviously and the effect is time-independent. The mechanism was clarified from H+ transport because AOP involved H+ production. The H+ transport was impeded under acid stress owing to the decrease of pH gradient across cell membrane. The two mechanisms formed a panoramic view of pH stress effect on nitrification advancing the understanding of nitrifier adaptability and nitritation regulation in wastewater treatment processes.

Integrated effects of operational temperature, HRT, and influent ammonium concentration on a CANON coupling with denitrification process treating for digested piggery wastewater: performance and microbial community.

In this study, an improved system called the completely autotrophic nitrogen removal over nitrite (CANON) process was presented and coupled with denitrification for the treatment of digested piggery wastewater (DPW). The effects of operating parameters, including hydraulic retention time (HRT) (1.6 d → 1.0 d), influent NH4+-N concentration (350 mg L-1 → 600 mg L-1), and temperature (41 â„ƒ → 17 â„ƒ), on the nitrogen removal performance and response characteristics of microbial population were investigated. Results showed that all considered parameters caused a remarkable effect on NH4+-N and total nitrogen removal efficiencies, and the chemical oxygen demand was more markedly affected by temperature. Candidatus_Kuenenia, Candidatus_Brocadia, Denitratisoma, norank_o_Xanthmonadales, norank_p_WWE3, and SM1A02 were the dominant genera influencing nitrogen removal in the improved CANON system for treating DPW. Redundancy discriminant analysis showed that the biological structure was positively correlated with the influent ammonium concentration, temperature, and HRT. The relative abundance of Candidatus_Kuenenia was perfectly correlated with HRT and temperature. However, environmental factors did not affect Candidatus_Brocadia and norank_p_WWE3. norank_c_Ardenticatenia, SM1A02, and norank_f_SJA-28 were all positively correlated with influent ammonium nitrogen concentration, but not correlated with HRT and temperature. The improved CANON process realized the nitrogen removal under high ammonium (NH4+-N) concentration and low C/N wastewater.

The phosphorus harvest from low-temperature mainstream wastewater through iron phosphate crystallization in a pilot-scale partial nitritation/anammox reactor.

The phosphorus harvest along nitrogen removal in the partial nitritation/anammox (PNA) reactor is promising for saving space and simplifying the management of mainstream wastewater treatment facilities. In this study, the phosphorus recovery from the low-temperature mainstream wastewater was explored through iron phosphate crystallization in a pilot-scale PNA reactor. With the COD-alleviated municipal wastewater as the influent, the ammonium concentration of about 50 mg/L and the phosphorus concentration ranged from 5.4 to 7.1 mg/L, under the temperature of 15 °C and the addition of external ferrous iron of 14 mg/L, the achieved nitrogen removal efficiency and the phosphorus removal efficiency were 37.6 % and 62.7 %, respectively. The good settleability of sludge indicated that the formed iron phosphate was well combined with the biomass. The quantitative analysis confirmed that the main iron phosphate in dry sludge was graftonite, and qualitative analysis confirmed that the equivalent of P2O5 content in the sludge was 5.8 %, which was suitable as fertilizer on agricultural land to realize the direct recycle of discharged phosphorus. In all, this study proposed a pioneering scheme to realize the nitrogen removal and phosphorus cycle in human society and given a meaningful reference for further research and application.

Molecular Insight into the Ionic Conduction of Quaternary Ammonium and Phosphonium Cation-Based Ionic Liquids Using Dielectric and Spectroscopy Analyses.

We analyzed the primary properties of ionic liquids (ILs) comprising quaternary phosphonium cations and bis(trifluoromethylsulfonyl) amide anions and compared them with those of corresponding quaternary-ammonium-cation-based ILs. Broadband dielectric spectroscopy was used to confirm the coupling between the translational and orientational motions of ions, and our results demonstrated that the high ionic conductivity of the phosphonium-based ILs was attributed to their fast rotational dynamics. The differences between ILs with different cations were further evaluated using vibrational (Raman and terahertz) spectroscopy. The Raman spectroscopy data revealed that the cation structure affected the conformation and flexibility (conformational change) of the anion. Furthermore, terahertz spectroscopy allowed us to evaluate the relationship between ion transport and intermolecular interactions between the cation and anion of ILs.

Interfacial silicon­nitrogen aerogel raise flame retardancy of bamboo fiber reinforced polylactic acid composites.

A triazine derivative containing nitrogen and silicon (SiN) was synthesized and the SiN hybrid aerogel was covered on the surface of bamboo fiber (BF). The modified BF was identified as MBF. The MBF and ammonium polyphosphate (APP) were used to regulate the flame retardancy and mechanical properties of polylactic acid (PLA). The PLA/BF composites were investigated using limiting oxygen index (LOI), UL-94 vertical combustion, cone calorimetry, thermogravimetric analysis linked with infrared spectra (TG-IR) etc. The char residue of MBF at 800 °C is as high as 43.5 % which is 200 % more than that of BF. Incorporating 9 wt% APP generates a PLA9 which displays the UL-94 V2 rating and a LOI value of 28.0 vol%. PLA9/MBF composites display the UL-94 V0 rating and increased LOI values while PLA9/BF composites obtain the UL-94 V2 rating and decreased LOI. The MBF reduces the release of flammable gases during combustion, enhances charring ability and decreases the thermal conductivity of composites. Besides, the tensile and impact strength of PLA9/20MBF is 20 % and 37 % more than that of PLA9/20BF due to stronger interfacial adhesion. This work provides a good method to regulate the flame retardancy and mechanical properties of PLA/BF composites.

Fenton oxidation of biochar improves retention of cattle slurry nitrogen.

Nitrogen (N) losses during fertilization with livestock slurry, mainly in the form of ammonia (NH3 ), can cause environmental problems and reduce fertilizer efficiency. Leonardite, which is characterized by oxygen-rich functional groups and low pH, has been found to decrease losses of slurry N. However, leonardite, as a byproduct of open-cast lignite mining, is not a renewable resource. The objective of this study was to modify biochar by chemical surface oxidation in order to find a sustainable but similarly effective substitute for leonardite. Biochar was produced from spruce sawdust in a pyrolysis oven at a maximum temperature of 610 °C. Then the biochar was oxidized using the Fenton reaction, with a ratio of Fe2+ /H2 O2 of 1:1,000, as a source of highly reactive HO· radicals to introduce oxygen-rich functional groups to the biochar surface. The ammonium (NH4 + ) adsorption capacity of biochar, oxidized biochar, and leonardite was tested in ammonium sulfate [(NH4 )2 SO4 ] solution, pH-adjusted (NH4 )2 SO4 solution, and cattle slurry. The results showed that biochar had the highest total NH4 + adsorption of 1.4 mg N g-1 in (NH4 )2 SO4 solution, whereas oxidized biochar had the highest reversible NH4 + adsorption of 0.8 mg N g-1 . In the pH-adjusted ammonium solution, all materials reduced NH3 emissions by ≥90%, and oxidized biochar reduced NH3 emissions by 99.99%. In contrast, leonardite reduced NH3 emissions the most in cattle slurry, and oxidation of biochar increased the reduction in NH3 emissions from 22 to 67% compared with non-oxidized biochar. In conclusion, biochar oxidized by means of the Fenton reaction greatly decreased NH3 emissions by increased adsorption of NH4 + in cattle slurry compared with non-oxidized biochar, indicating the great potential of oxidized biochar for reducing N losses during slurry application.

Enhanced nitrogen removal in mainstream deammonification systems at ambient temperature by novel modified carriers and differentiation of microbial community transformation.

Zeolite-modified polyurethane (ZP) carriers and zeolite/tourmaline-modified polyurethane (ZTP) carriers were proposed to enhance mainstream deammonification. The system with ZTP carriers was rapidly established in 28 days with a nitrogen removal rate (NRR) of 0.150 kg N·(m3·d)-1. Moreover, the facilitative effect of tourmaline was suggested by the highest humic acid peak intensity and more balanced potential activity. Besides, SEM-EDS analysis revealed carrier characteristic improvement was achieved in both novel carriers while maintaining an excellent spatial structure. Moreover, the microbial analysis suggested that both modified carriers support the substrate supply to anaerobic ammonium oxidizing bacteria (AnAOB) by enhancing dissimilatory nitrate reduction to ammonium and partial denitrification under nitrate accumulation conditions. Nevertheless, the ZTP system had a greater advantage over maintaining the original AnAOB (Candidatus Jettenia) and ammonium oxidizing bacteria (Nitrosomonas) abundance. Overall, this study provides ZTP carriers with great potential for facilitating the establishment of mainstream deammonification at full-scale WWTPs.

Enhanced fire-proofing performance and crystallizability of bio-based poly(L-lactic acid): Dual functions of a Schiff base-containing synergistic flame retardant.

Poly(L-lactic acid) (PLA) is a kind of important bio-macromolecule which can be prepared via fermentation of starch of maize and sweet potato. Flammability and extremely poor crystallizability limited its wide application. In this work, a novel Schiff base derivate (CP) was synthesized and, combined with ammonium polyphosphate (APP) as a synergistic flame retardant and nucleating agent to investigate its effects on LOI, UL-94 rating, thermal stability, combustion behavior and crystallizability of PLA. With loading of 5%CP/10%APP, PLA showed a significantly enhanced LOI and passed V-0 fire-safety rating with self-extinguish effect. PLA/5%CP/10%APP presented the lowest pHRR, THR and TSR, and highest char residue yield, FPI and FRI in cone calorimetry test, indicating an excellent flame retardancy effect, enhanced fire safety and longer escaping time in the fire. A continuous, compact and thick char layer structure formed as a protective barrier in combustion process, to enhance heat-insulating and oxygen resistance property, thermal stability and smoke-suppressing capacity of PLA. Flame retardancy mechanism was proposed and discussed based on comprehensive and in-depth characterization techniques. Also, 5%CP/10%APP presented a good nucleation effect to enormously increase crystallizability and shorten crystallization time of PLA.

Adsorption behavior and mechanism of amine/quaternary ammonium lignin on tungsten.

Amine/quaternary ammonium lignin for adsorption of tungsten was synthesized by amination and quaternization from lignin. The adsorbent was characterized by SEM-EDS and FTIR. The effects of pH, initial concentration of tungsten, adsorption time and dosage of adsorbent on the adsorption effect were investigated. The adsorption mechanism was revealed by SEM-EDS and FTIR and XPS. The results showed that amine/quaternary ammonium lignin was loose and rough and contained a large number of phenolic hydroxyl and amine and quaternary ammonium functional groups. Using the optimum conditions, which included the pH of 4.0 and initial tungsten concentration of 800 mg·L-1 and adsorption time of 960 min, the saturated adsorption capacity of 1 g·L-1 amine/quaternary ammonium lignin for tungsten reached 421.68 mg·g-1. The adsorption followed Langmuir model and quasi-second-order kinetic model, indicating that the adsorption was monolayer homogeneous chemisorption. When the total concentration of tungsten was 0.005 mol·L-1 and the value of pH was smaller than 4.7, H2W12O406- was the existing form of tungsten and was adsorbed by electrostatic attraction of hydrogen bond and coordination with amino and ion exchange with Cl-.