Humic Research Articles

A Strategy for Quantifying Microplastic Particles in Membrane Filtration Processes using Flow Cytometry

Microplastic (MP) pollution is ubiquitous in the aquatic environment, with significant quantities of MPs originating from municipal wastewater treatment plants. Efforts to evaluate and implement MP removal processes are underway, with membrane technologies often recommended as an "ideal" solution. A key challenge in evaluating these technologies involves efficiently quantifying MP concentrations in samples. Here, flow cytometry (FC) is demonstrated as an effective technique to obtain concentration measurements of plastic microbeads (MBs; 1-5 μm) suspended in water with/without added humic acid. Regardless of solution conditions, MB concentrations were easily quantified via FC. Subsequently, two microfiltration membranes were challenged to these suspensions. As measured via FC, the 0.45 μm membrane demonstrated effective MB rejection (>99%) whereas the 5 μm membrane exhibited a broad range of rejections (40% to >95%) depending on solution conditions and filtration time. Finally, a model was formulated utilizing FC forward light scattering intensity measurements to estimate MB sizes in samples. Using the model, a 33% reduction in median MB size, on average, was noted across the 5 μm membrane when filtering MBs suspended in humic acid solution, affirming a preferential permeation of smaller particles. Overall, this study advances MP quantification techniques towards validating removal processes.

Removal of nitrate nitrogen by aerobic denitrification granular sludge under strongly alkaline conditions: Performance and mechanism

Aerobic granular sludge (AGS) technology faces challenges in treating strongly alkaline wastewater because high pH affects sludge settleability and microbial metabolic activity. In this study, aerobic denitrification granular sludge (ADGS) was cultivated with strongly autoaggregating aerobic denitrifying bacteria as the sludge source at an influent pH of 11.0 under aerobic conditions. The formation characteristics of ADGS and its pollutant removal efficiency under strongly alkaline conditions were explored. Compared with ADGS cultivated under neutral conditions, ADGS cultivated under strongly alkaline conditions resulted in superior particle formation rates, settleability, particle strengths and particle stabilities. Nitrate nitrogen was almost completely removed at a pH of 11.0 under aerobic conditions. Protein, polysaccharides and humic acid in extracellular polymeric substances (EPS) under strongly alkaline conditions were involved in the ADGS formation process. In addition, the presence of metallic elements in the EPS and inorganic nuclei in the sludge facilitated the formation of ADGS. The strongly alkaline environment enriched the alkali-resistant aerobic denitrifying bacteria, such as unclassified_f__Rhodobacteraceae, Tessaracoccus, Halomonas, and Pseudofulvimonas, as well as specialized alkali-resistant genera. Furthermore, the strongly alkaline environment increased the abundance of key enzymes involved in carbon metabolism and upregulated the expression of nitrogen metabolism genes in the ADGS to maintain their metabolic activity. In addition, the microorganisms upregulated genes that encoded reverse transporter protein genes (mnhACEFG, nhaACP, and phaACDEFG) and K+ uptake protein genes (trkAHG) and secreted greater amounts of acidic functional groups and free amino groups to help maintain intracellular and extracellular osmolality and acid–base homeostasis under strongly alkaline stress. This research provides a possible option and innovative strategy for the management of highly alkaline nitrate-containing wastewater.

Sequential DBD plasma-assisted tandem tri-electrodes Fenton process for enhanced antibiotics treatment and denitrification

Ozone generated by dielectric barrier discharge (DBD) plasma has the potential for water treatment; however, its limitations, including water solubility, performance in complex matrices, and resistance to some pollutants. This study explored a sequential DBD plasma assisted by a tandem tri-electrode Fenton (S-PEF) process, using a three-stage treatment approach for degrading antibiotics (sulfamethoxazole, SMX; amoxicillin, AMX; and norfloxacin, NOF) in continuous flow mode for 220-bed volumes. Initially, antibiotics such as SMX and AMX underwent degradation in DBD plasma gas, which housed the mixing chamber. The more resilient NOF was removed by hydroxyl radicals (OH) in the following anodic chamber of the tandem trielectrodes by Fenton assisted oxidation. The continuous cyclic redox regeneration of Fe in tandem trielectrodes prevents secondary Fe sludge pollution. Finally, NO3-N and NO2-N were denitrified into N2 with 95 % selectivity in a cathodic chamber using copper oxide nanowires. This sequential treatment is crucial to mitigating the competitive effects of CO32− and humic acid in wastewater since O3 is less susceptible to them compared to OH. The S-PEF completely degraded all antibiotics regardless of water temperature (10 and 25 °C) compared to sole plasma treatment. Finally, toxicity assessments using an ecological structure–activity relationship (ECOSAR) and E. coli disinfection assays showed a significant reduction in toxicity. This study highlights the promising potential of the S-PEF as an advanced technology for wastewater treatment.

Co-doped NH2-UiO-66 for fast and effective adsorption of oxytetracycline: Kinetics, thermodynamics and mechanism

Novel type of micro mesoporous materials Co-doped NH2-UiO-66 had been successfully prepared. The properties of the material were understood through a series of characterization. When the dosage of Zr:Co is 2:1, the modified material showed specific surface area of 840.02 m2∙g−1, which is larger than the material without Co. Especially, the material was transformed from microporous NH2-UiO-66 to micro-mesoporous Co-doped NH2-UiO-66 through the adjustment of metal Co. The Co-doped nanocomposite was then applied to the adsorption of oxytetracycline. The effects of initial concentration, pH, humic acid and ionic strength on the adsorption were investigated. It was found that 50 mg∙L−1 oxytetracycline can be effectively adsorbed by Co-doped NH2-UiO-66 in pH 7. Further research showed that adsorption was pseudo-second-order kinetics and fitted Freundlich model with the maximum adsorption capacity 223.7 mg∙g−1. In addition, the adsorption equilibrium time was only 2 h, which is shorter than the adsorption time of most adsorbents. The mechanism of pore adsorption, π-π interaction, hydrogen bonds and electrostatic interactions was deeply discussed. In conclusion, Co-doped NH2-UiO-66 was a fast and effective absorbent for the removal of oxytetracycline in aqueous solution.

CO2(OH)2CO3 and Fe doped Co2(OH)2CO3 prepared as efficient and stable catalysts for activation of PMS: Two systems comparison and key role of high-valent metal-oxo species in mechanism revealing

High-valent metal-oxo species [M(IV) = O] exhibited high selectivity and chemical efficiency in advanced oxidation processes for removing organic pollutants, making their manipulation essential in catalytic systems. However, the low and unsustainable efficiency of generating M(IV) = O posed significant challenges. In this research, Co2(OH)2CO3 were successfully prepared via a one-pot hydrothermal method to efficiently activate peroxymonosulfate (PMS) with high-valent cobalt-oxo species [Co (IV) = O] as the primary active oxidation species. Building upon this foundation, COC was modified through variations in metal types and elemental ratios, in which magnetically enriched FexCo2-x(OH)2CO3 was synthesized by gradient Fe doping with higher catalytic efficiency and stability. The insertion of Fe resulted in the lengthening of the Co-O bond and improved the valence distribution of cobalt on the COC surface. Besides, it enabled part of the electrons to be transferred from the Fe active center to the Co active center, breaking the limitation of the traditional two-electron transfer and realizing the stable generation of more high-valent metals. Both reaction systems achieved efficient degradation of sulfadimethoxine (SDM) within 30 min and were able to completely degrade SDM within 30 min even after three cycles. FexCo2-x(OH)2CO3 maintained excellent catalytic performance even after 30 days of exposure to air. In both systems, high-valence metals played a dominant role, while the contributions of hydroxyl radicals and sulfate radicals were negligible. Overall, the two groups of developed catalysts both showed remarkable stability and pollutant removal performance in anions, humic acid, Different antibiotics and real water systems, which provided a new perspective on antibiotic removal.

Impact of organic matter constituents on phosphorus recovery from CPR sludges.

This study evaluated the influence of organic matter (OM) constituents on the potential for recovery of P from wastewaters when FeCl3 treatment is employed for P removal. The presence of OM constituents did not influence P release from Fe-P sludges when alkaline and ascorbic acid treatments were employed. However, the overall recovery of P from wastewater was impacted by the presence of selected OM constituents through the reduction of P uptake during coagulation. The presence of protein and humic matter showed remarkably low P removal values (3.0±0.4% and 23 ±1% respectively) when compared to an inorganic control recipe (62 ±2%). Elevated soluble Fe (SFe) residuals in the presence of proteins (87 ±5%) and humics (51 ±1%) indicated interactions between Fe(III) cations and negatively charged functional groups like hydroxyl, carboxyl, and phenolic groups available in these organics. Significant negative correlations between P removal and residual SFe were observed suggesting Fe solubilization by OM constituents was the mechanism responsible for reduced P removal. The findings of this study identify, for the first time, the impact of OM constituents on overall P recovery when Fe(III) salts are employed and provide insights into recoveries that can be expected when Fe is added to primary, secondary treated, and industrial wastewaters. PRACTITIONER POINTS: Low P removal values were observed for protein and humic dominated wastewater recipes. Iron(III) solubilization counted for P removal reduction by proteins and humic acids. There is no effect of OM on P release from Fe-P sludge at pH 10 and ascorbic acid treatments. OM and agent employed to release P from sludges affected overall recovery of P.

Nano-magnetite enhances dissimilated iron reduction to vivianite from sewage by structuring an enormous and compact electron transfer network

Acting as both terminal and conductor of extracellular electron transfer (EET), little studies were focused on how nano-magnetite participated in the dissimilated iron reduction (DIR), especially the synthesis of vivianite, which was the typical DIR products from sewage. In this study, nano-magnetite was confirmed to enhance DIR of ferrihydrite and akaganeite for vivianite recovery from sewage. Nano-magnetite incorporation enriched Comamonas and Geobacter in sewage, and microbial protein content was increased by 123 % and 57 % in ferrihydrite and akaganeite batches, respectively. In Geobacter sulfurreducens PCA pure culture, vivianite yield was promoted by 21 % and 37 % in ferrihydrite and akaganeite batches in the presence of nano-magnetite, respectively. Due to its nanoscale size and superior electrical conductivity, nano-magnetite embedded in the gaps formed by the microorganisms and electron acceptor, and architected coherent conductive pathways to promote EET. Simultaneously, the addition of nano-magnetite stimulated the secretion of proteins, polysaccharides, and humic acids in the extracellular polymeric substances. Nano-magnetite addition structured an enormous and compact electron transfer network, thus enhanced DIR and vivianite formation. Our study proposed a new strategy to promote iron-reduction-coupled phosphorus recovery with natural DIR products, and provided theoretical support for clarifying the interaction between minerals and microorganisms.

Near-Complete Phosphorus Recovery from Challenging Water Matrices Using Multiuse Ceramsite Made from Water Treatment Residual (WTR)

Water treatment residual (WTR) is a burden for many water treatment plants due to the large volumes and associated management costs. In this study, we transform aluminum-salt WTR (Al-WTR) into ceramsite (ASC) to recover phosphate from challenging waters. ASC showed remarkably higher specific surface area (SSA, 70.53 m2/g) and phosphate adsorption capacity (calculated 47.2 mg P/g) compared to previously reported ceramsite materials (< 40 m2/g SSA and < 20 mg P/g). ASC recovered over 94.9% of phosphate across a wide pH range (3 – 11) and generally sustained > 90% of its phosphate recovery at high concentrations of competing anions (i.e., Cl-, F-, SO42-, or HCO3-) or humic acid (HA). We challenged the material with real municipal wastewater at 10°C and achieved simultaneous phosphate (>97.1%) and COD removal (71.2%). Once saturated with phosphate, ASC can be repurposed for landscaping or soil amendment. The economic analysis indicates that ASC can be a competitive alternative to natural clay-based ceramsite, biochar, or other useful materials. Therefore, ASC is an eco-friendly, cost-effective adsorbent for phosphate recovery from complex waters, shedding light upon a circular economy in the water sector.

Photochemical Transformation of Ibuprofen and Chlorophene Induced by Dissolved Organic Matter.

Both ibuprofen (IBP) and chlorophene (CP) are frequently detected contaminants in surface aqueous environment. Dissolved organic matter (DOM) is an important component in water with high photo-reactivity, playing an important role in the transformation processes of various organic pollutants. This study systematically studied the influence of DOM on the photochemical transformation of IBP and CP by using humic acid as model DOM. In addition, the effect of inorganic salts on this process is also considered due to the high salt content in the ocean. Further quenching experiments and reactive oxygen species (ROSs) detection were also conducted to explore the reactive species acting on the IBP and CP transformation. Based on the products analysis and theoretical calculation, we proposed the IBP and CP transformation mechanism. Overall, this study provides some new insights into the transformation of organic pollutants in natural surface water, which is significant for assessing the fate of pollutants.

Impact of biofertilizers and humic acid on growth of ornamental coleus

Impact of biofertilizers and humic acid on growth of ornamental coleus

Molecular insights into the binding mechanism of strontium and cesium on phyllosilicates with different expandability

The environmental fate of strontium (Sr) and cesium (Cs), as the critical radioactive fission products, have raised significant concerns regarding radioactive waste disposal and environmental protection. The current study investigated the distinction in the binding configurations of Sr2+ and Cs+ on various 2:1 phyllosilicate (illite, vermiculite, and montmorillonite) by combining batch adsorption, sequential extraction, and spectroscopic analyses. The results show that strontium adsorption is strongly influenced by pH as well as ionic strength, while there is no significant variability in strontium adsorption by different types of clay minerals. EXAFS analysis confirms the outer complexation of strontium on the planar sites of the clay minerals, i.e., Sr2+ is surrounded by ~8.0 O atoms, RSr-O ≈ 2.6 Å, and that process is mainly realized by ion exchange. In contrast, Cs+ adsorption was markedly influenced by the variety of clay minerals but less by pH and ionic strength, the presence of humic acid (HA) inhibited Cs+ adsorption. The inner-sphere complexation formed mainly at the frayed edge sites on illite, and interlayer sites on vermiculite and montmorillonite, was the dominant mechanism for Cs+ adsorption. In addition, the collapse of the interlayer space of vermiculite induced by Cs+ adsorption on the interlayer sites was responsible for the more stable and irreversible immobilization. The findings in present work highlighted the significance of prevailed mineral in governing environmental migration risk of radionuclides, the revealed adsorption mechanism and binding configuration of Sr2+ and Cs+ on typical phyllosilicates would be referable in constructing a reliable migration model of Sr2+ and Cs+ in natural media.

High-capacity and long-life Fe2O3/MOFs composite anodes: Preparation, characterization, morphology regulation and electrochemical performance

Among the various transition metal oxides used in lithium-ion battery anodes, iron oxide (Fe2O3) has received extensive attention due to its low cost, good environmental compatibility and high theoretical capacity. However, the volume expansion and structural collapse during the charging-discharging cycling process significantly limited the practical application of Fe2O3. Herein, we demonstrate enhanced electrochemical properties and stability of Fe2O3 by anchoring it on metal-organic frameworks (MOFs). Through adjusting the MOF ligands and introducing humic acid (HA), we reached rational control of the morphology for the Fe2O3/MOF composites. The optimized sample, namely Fe2O3@HA-Fe-ATA, shows 3D cauliflower-like structure with abundant pores, which are beneficial to the active sites exposure, electrolyte penetration, as well as the tolerance toward volume expansion. Consequently, high reversible capacity of 1442.7 mAh g−1 (at 0.1 A g−1), excellent rate performance (<11 % capacity decrease when current density increases from 0.1 A g−1 to 1 A g−1), and satisfactory cycle stability (91 % capacity retention after 500 cycles at 1 A g−1) are obtained. This work demonstrates that the rational design of MOF by introduction of appropriate ligand is a very efficient approach to optimize the electrochemical properties of the resultant electrode material.

The interplay of Brown carbon (BrC) surrogates and copper: Implications for the oxidative potential of ambient particles

Atmospheric particulate matter (PM) poses adverse effects on human via producing reactive oxygen species (ROS). Oxidative potential (OP, ability to generate ROS) can be induced by various chemicals in PM, while their interplay remains poorly characterized. Here, we systematically assessed influences of Cu2+ on OP of Brown carbon (BrC) (e.g., imidazoles) using dithiothreitol (DTT) assay. Results showed DTT consumption rate exhibited an initial rise and later decline (0.25 −0.56 µM/min) along with increase of BrC concentration (0.1 − 2 µM), while no general trend was observed for •OH formation. Although Cu2+ showed either antagonism or synergism with BrC against DTT consumption, Cu2+ displayed antagonism with most BrC against •OH generation. Fluorescence quenching experiments provided evidence of complexation between Cu2+ and water-soluble organic compounds (WSOCs, from ambient PM2.5), which was influenced by Cu2+ concentration. Further parallel factor analysis of spectra showed that polycarboxylate-type humic acid-like substances (complexation site number (n): 0.46, complexation equilibrium constant (k): 0.51) and fulvic acid-like compounds (n: 0.42, k: 0.62) were the main components in WSOCs that complexed with Cu2+. Our results suggest the interactions of BrC and copper play a crucial role in PM OP and highlight complexation in evaluation of PM OP.

Deciphering origins of hydrocarbon deposits by means of intramolecular carbon isotopes of propane adsorbed on sediments

Hydrocarbons are one of the important fluids within the Earth’s crust, and different biotic and abitoic processes can generate hydrocarbon during geological periods. Tracing the sources and sinks of hydrocarbons can help us better understand the carbon cycle of the earth. In this study, an improved approach of adsorbed hydrocarbons extraction from sediments was established. The improved thermal desorption approach, compound-specific isotope analysis and position-specific isotope analysis were integrated to investigate the molecular and intramolecular isotope fractionation between trace hydrocarbon gases within sediments and geological hydrocarbon deposits. The isotopic compositions of the terminal position carbon of propane (δ13Cterminal) serves as a correlation indicator between trace hydrocarbon gases within sediments and geological hydrocarbon deposits. The tight sandstone gas from the Turpan-Hami Basin is a first case study for the application of this novel method to trace hydrocarbon origins. The results showed that the hydrocarbons in the tight sandstone gases in the study area most likely originated from humic organic matter (type III kerogen) at an early mature stage. δ13Cterminal values of the thermally desorbed propane gases from different source rocks were distinguishable and the values of the tight sandstone gases significantly overlap with those of the Lower Jurassic Sangonghe source rocks, suggesting their genetic relationship. Overall, the results provided novel position-specific carbon isotopic constraints on origins of hydrocarbons.

Toxicological and mechanistic insights into organic contaminants released from on-line membrane cleaning during ultrafiltration of algal-containing waters

Eutrophication has significantly challenged the treatment of algae-contaminated water. Ultrafiltration has become an essential method for water purification, though frequent on-line chemical cleaning is necessary to maintain membrane permeability. This study aims to systematically investigate the impact of various chemical cleaning agents on the release of dissolved organic matters and toxic by-products, particularly from algal cells. Through a series of controlled experiments, Microcystis aeruginosa cells were exposed to different cleaning agents (HCl, NaOH, NaClO), and the resulting DOM and by-products were characterized. Special attention was paid to the release of intracellular organic matter (IOM) and extracellular organic matter (EOM). Results revealed that NaClO significantly oxidized IOM, leading to the formation of humic-like substances and halogenated organic compounds (TOX), including 15 types of halogenated by-products detected by UPLC/ESI-tqMS. Furthermore, the release of toxic microcystin LR (MC-LR) was traced primarily to IOM. The removability of these contaminants by UF and reverse osmosis (RO) membranes was analyzed, revealing that over 50% of the toxic by-products passed through UF membranes, and 10% still penetrated RO membranes, raising significant concerns for downstream water quality and drinking water safety.

Optical characteristic of dissolved organic matter polar fractions by spectrum technologies and the relationship with indirect photodegradation of ofloxacin

Ofloxacin (OFL) is a commonly used antibiotic and is widely present in various water bodies. Indirect photodegradation is crucial for the transformation and fate of antibiotics in surface water, which largely depends on the structure and composition of dissolved organic matter (DOM). Nevertheless, knowledge about the optical characteristics of diverse DOM polar fractions as well as the relationship with indirect photodegradation of antibiotics is still scarce. In this study, XAD-8 in combination with anion and cation exchange resins was used to separate DOM into six polar fractions: hydrophilic acid (HIA), hydrophilic basic (HIB), hydrophilic neutral (HIN), hydrophobic acid (HOA), hydrophobic basic (HOB) and hydrophobic neutral (HON). UV–vis and fluorescence spectroscopy were applied to analyze DOM polar fractions and explore their impact on OFL indirect photodegradation. The results showed that indirect photodegradation was the primary photodegradation route of OFL when the irradiation wavelength was greater than 320 nm, triple-state excited DOM (3DOM*) was the main reactive intermediates (RIs) that affected the indirect photodegradation of OFL. Excitation-emission matrix spectroscopy combined with parallel factor analysis (EEMs-PARAFAC) and correlation analysis demonstrated that terrestrial humic-like substances could yield generous RIs to facilitate OFL indirect photodegradation. The HIB and HOA fractions of SRNOM contained large aromaticity and humification degree and more terrestrial humic-like substances, thus exhibiting greater OFL indirect photodegradation rates. The HOA and HOB fractions of FA had abundant terrestrial humic-like substances and contributed more to OFL indirect photodegradation. This study helped us understand the effect of DOM structural characteristics on the OFL indirect photodegradation.

Revealing the interplay of dissolved organic matters variation with microbial symbiotic network in lime-treated sludge landscaping

Lime pretreatment is commonly used for sludge hygienization. Appropriate lime dosage is crucial for achieving both sludge stabilization (lime dosage >0.2 g/g-TS) and promoting plant and soil health during subsequent landscaping (lime dosage <0.8 g/g-TS). While much research has been conducted on sludge lime treatment, few studies have examined the effects of lime dosing on integrating sludge stabilization and plant growth promotion during landscaping. In this study, we investigated microbial dynamics and dissolved organic matter (DOM) transformation during sludge landscaping with five lime dosage gradients (0, 0.2, 0.4, 0.6, 0.8 g lime/g-TS) over 90 days. Our results showed that a lime dosage of 0.4 g/g-TS is the lower threshold for achieving waste activated sludge (WAS) stabilization during landscaping, leading to maximum humic substance formation and minimal phytotoxicity. Specifically, at 0.4 g/g-TS lime dosage, protein degradation and decarboxylation-induced humification were significantly enhanced. The predominant microbial genera shifted from Aromatoleum to Exiguobacterium and Romboutsia (both affiliated with the phylum Firmicutes). Reactomics analysis further indicated that a 0.4 g/g-TS lime dosage promoted the hydrolysis of proteins (lyase reactions on C-C, C-O, and C-N bonds), amino acid metabolism, and decarboxylation-induced humification (e.g., C1H2O2, C2H4O2, C5H4O2, C6H4O2). The co-occurrence network analysis suggested that the phyla Firmicutes, Proteobacteria, and Bacteroidetes were key players in DOM transformation. This study provides an in-depth understanding of microbe-mediated DOM transformation during sludge landscaping and identifies the optimal lime dosage for improving sludge landscaping efficiency.

Construction of a multiple reactive species-mediated Co9S8/NBC-PMS Fenton-like system for tetracycline degradation with broadened adaptability to water background

A Fenton-like system based on peroxymonosulfate (PMS) oxidant has high potential for antibiotic degradation, However, various complex water background factors, including pH, coexisting ions, and dissolved organic matter, can adversely affect degradation efficiency. This work constructed a PMS oxidative Fenton-like system activated by cobalt polysulfide/N-doped biochar composite (Co9S8/NBC) for the degradation of tetracycline (TC) and achieving approximately 99 % removal of TC. Furthermore, the removal efficiency was maintained above 90 % across a broad pH range (3−11), in the presence of various coexisting anions (Cl−, NO3− and CO32−), even at high concentrations of humic acid. The characterization of Co9S8/NBC through various techniques confirmed that Co9S8 nanoparticles were uniformly loaded within the porous NBC structure. Electron paramagnetic resonance and reactive oxygen species (ROSs) quenching experiment revealed that the effectiveness of TC degradation in the Co9S8/NBC/NBC-PMS system arises from the cooperation of radical and non-radical species rather than the single mechanism. Moreover, the analysis of the contribution ratios of ROSs to TC degradation indicates that the contribution of non-free radicals exceeds that of free radicals, and it is capable of adapting to changes in pH. The characterization of the post-reaction catalyst suggested that Co9S8 and NBC synergistically participated in the activation of PMS. Moreover, the practical examination proved that the disabled Co9S8/NBC catalyst can recover the catalytic activity via a reheat treatment, the leaching concentration of Co ions was lower than the emission limit of China. The river water and lake water as the matrix water have little negative impact on the degradation of TC. The Co9S8/NBC-PMS system is expected to provide a practical pathway for the treatment of antibiotic wastewater.

Response of nitrifiers to gradually increasing pH conditions in a membrane nitrification bioreactor: Microbial dynamics and alkali-resistant mechanism

Nitrification and nitrifiers are pH-sensitive especially under the alkaline environment in the activated sludge system. However, it is unclear how nitrifiers and nitrification respond to long-term alkaline environment. This study employed a continuous flow membrane nitrification bioreactor to investigate the dynamics of nitrification efficiency and microbial community adaptation under a 320-day alkaline operation. Results showed that activated sludge adapted remarkably to a progressive increase in pH from 7.5 to 10.0, achieving robust nitrification with average ammonia removal efficiencies of 96.6 ± 2.2%. Subsequently, an integrated alkali-resistant mechanism of nitrifiers was proposed. Specifically, under the long-term operation of pH 10.0, certain bacteria secreted enhanced extracellular acidic polysaccharides (i.e., up to 10.95 ± 0.27 mg·g−1 MLVSS in soluble extracellular polymeric substances (EPS)) and acidic organic compounds (e.g., humic acids increased by 1.47-fold in tightly bounded EPS) to neutralize external alkalinity. Moreover, significant enrichments in both the ammonia oxidizing bacteria Nitrosomonas (by 1.3%) and the nitrite oxidizing bacteria Nitrospira (by 5.4%) were observed in a 170-day operation of pH 10.0 condition. Meanwhile, norank_f__JG30-KF-CM45 (2.0%) and Rhodobacter (0.9%) also contributed to ammonia removal at pH 10.0. On the cellular-level, bacteria enabled to maintain intracellular pH stabilization primarily through cation/proton antiporters, evidenced by significant increases in NhaA, TrkA and KefB activities by 98.0%, 151.7% and 115.2%, respectively. A 43.1% increase in carbonic anhydrase activity also facilitated consumption of aqueous OH− ions through biomineralization, leading to CaCO3 deposition on microbial surface. These findings further enhanced understandings of physiological adaptation of nitrifiers in the long-term alkaline activated sludge system.

Mechanism of carbonized humic acid and magnesium aluminum-layered double hydroxide promoting biohydrogen generation

Dark fermentation (DF) is prone to low hydrogen (H2) yield. In this work, magnesium aluminum-layered double hydroxide and carbonized humic acid (MgAl-LDH/CHA) was synthesized by co-precipitation to reveal the mechanism in rising bioH2 generation. The results indicated that MgAl-LDH released Mg and Al ions slowly in DF system, improving the activity of H2-producing microbes (HPM) for more H2. The H2 yield increased from 169.3 mL/g glucose to 244.9 mL/g glucose, which was 44.7 % higher than that for the control yield. MgAl-LDH/CHA increased Proteobacteria content from 30.9 % to 43.7 %, making it form a complex microbial community and participate in DF metabolism with Firmicutes and other microbes together. Besides, MgAl-LDH/CHA could serve as an electron shuttle that likely effectively promotes electron transfer in DF, significantly reduced the energy requirements of HPM, thus raising metabolic activity. It provides direction for the multi-element composite applied in DF system.