Fast start-up anammox process using Acyl-homoserine lactones (AHLs) containing supernatant.

N-dodecanoyl homoserine lactone (C12-HSL) was detected in the supernatant of an anammox granular sludge reactor (AGSR). C12-HSL could enhance the specific anammox activity of anammox biomass. Adding C12-HSL-containing AGSR supernatant into the continuously stirred tank reactors reduced the start-up time of the anammox process from 80 to 66days. Moreover, the nitrogen loading rate was also enhanced to 1.6 times that of the control reactor. AHLs could increase the secretion of extracellular polymeric substances and anammox obtained better enrichment with the addition of AHLs-containing AGSR supernatant. Denaturing gradient gel electrophoresis analysis further revealed that AHLs played a role in mediating microbial community parameters. In conclusion, adding AHL-containing supernatant could be an effective and economical way to accelerate the start-up of anammox.

Effects of Inhibiting Acylated Homoserine Lactones (AHLs) on Anammox Activity and Stability of Granules'.

In this study, the effects of AHL-based QS signals on anammox activity and stability of granules' were investigated. Results clearly showed that the vanillin and porcine kidney acylase I could reduce the AHLs in anammox bacteria. Inactivation of AHLs by vanillin and porcine kidney acylase I depressed the nitrogen removal ability of anammox bacteria. A significant inhibition of specific anammox activity was observed when the concentration of vanillin and porcine kidney acylase I increased to 1 g/L. Anammox activity was depressed on enzyme level. Moreover, degradation of AHLs under vanillin and AHL-acylase exposure could result in anammox granules' disintegration. Further research showed that the contents of protein (PN) and polysaccharides (PS) in extracellular polymeric substances were reduced with AHLs blocked, and it further explained the instability and weakening strength of the anammox granules. The results of our investigation provided new insight into the AHL-based QS-regulated anammox activity, leading a potential way to enhance stability of anammox granules.

Research of iron reduction and the iron reductase localization of anammox bacteria.

The iron-reducing capability of anammox bacteria was examined in this study using Percoll purified anammox bacteria. Anammox bacteria could reduce Fe(III) to Fe(II) with organic matters as the electron donor. The activity of anammox iron-reducing process was dependent on different electron donor, acceptor and pH. The highest iron-reducing activity of anammox bacteria was achieved with Fe(III)-NTA (nitrilotriacetic acid) as electron acceptor and formate as the electron donor at pH7. Similar to other iron reducers, 80 % of the iron reductase in anammox bacteria was located in the membrane fraction. Due to the chemical oxidant of NO2 (-) and the NO3 (-) dependent ferrous iron oxidation by anammox bacteria, the iron-reducing activity of anammox bacteria could be severely inhibited when iron-reducing pathway and the anammox process were coupled. However, the total nitrogen removal efficiency was not significantly affected in the presence of Fe(III). The iron-reducing capability of anammox bacteria could influence both N and Fe cycle on earth, and it is a potential way for wastewater treatment.

Optimal cultivation of simultaneous ammonium and phosphorus removal aerobic granular sludge in A/O/A sequencing batch reactor and the assessment of functional organisms.

In this study, sequencing batch reactor (SBR) with an anaerobic/aerobic/anoxic operating mode was used to culture granular sludge. Optimal adjustment of cycle duration was achieved by the direction ofpH, oxidation reduction potential and dissolved oxygen parameters. The results showed that the treating efficiency was significantly improved as the cycle was shortened from 450 to 360 min and further to 200 min. Nitrogen and phosphorus removal were nearly quantitative after 50 days operation and maintained stable to the end of the study period. The typical cycle tests revealed that simultaneous denitrification and phosphorus removal occurred when aerobic granules were gradually formed. The nitrite effect tests showed that less than 4.8 mg N/L of the nitrite could enhance superficial specific aerobic phosphate uptake rate (SAPUR) under aerobic condition, indicating that the traditional method to evaluate the capability of total phosphate-accumulating organisms (PAOs) was inaccurate. Additionally, a high level of nitrite was detrimental to PAOs. A novel method was developed to determine the activity of each kind of PAOs and other denitrifying organisms. The results showed that (1) nitrate, besides nitrite, could also enhance SAPUR and (2) aerobic granular sludge could perform denitrification even when phosphate was not supplied under anoxic condition, suggesting that other denitrifying organisms besides denitrifying phosphate-accumulating organisms also contributed to denitrification.

[Prenatal ultrasonic manifestation and clinical significance of fetal hemivertebra].

OBJECTIVE: To explore the manifestation and clinical significance of prenatal ultrasound diagnosis of fetal hemivertebra. METHODS: In the study, 27 fetals with hemivertebras (proven by post-natal X-ray, CT or MR) were examined by prenatal ultrasound and MR in Women & Children's Hospital, Ningbo, Zhejiang. Two-dimensional and three-dimensional prenatal ultrasonic manifestations were retrospective analyzed and compared with the prenatal MR diagnoses, the post-natal X-ray, CT, MR examinations. All the fetuses were carried out karyotype examinations. The full-term births recieved surgical treatment and the Cobb angle correction rate was calculated. RESULTS: The 27 cases of fetal ultrasound showed the morphological changes of the spine, with the involved segment only half of the vertebra, in which 9 cases were single hemivertebra and 18 cases multiple, 8 cases were no malformation and 19 cases other malformations, and 19 cases were induction of labor, and 8 cases of term delivery. Compared with postpartum X-ray and other imaging tests, the prenatal ultrasound accuracy rate was 92.5%, and prenatal MR 96.3%. In the 27 cases, the chromosome cultures of 25 cases were successful, in which the normal karyotype was 68.0% (17/25), and abnormal karyotype 32.0% (8/25) with multiple hemivertebra accounting for 47.1% (8/17). In 8 cases with posterior approach of hemivertebra resection, 6 patients were less than and equal to 3 years old, whose average Cobb angle correction rate was 38.02%, and 2 more than 3 years old, whose average Cobb angle correction rate was 24.98%. CONCLUSION: Fetal hemivertebra have typical sonographic manifestations. In diagnosis of fetal hemivertebra, the accuracy of prenatal ultrasound is close to that of MR, which has important clinical implications in diagnosis and overall assessment of fetal hemivertebra, and can also provide appropriate clinical genetic reference.

Calcined pyrite accelerates sulfur metabolic and electron transfer in driving targeted microbial fuel cell denitrification.

The sulfur powder as electron donor in driving dual-chamber microbial fuel cell denitrification (S) process has the advantages in economy and pollution-free to treat nitrate-contained groundwater. However, the low efficiency of electron utilization in sulfur oxidation (ACE) is the bottleneck to this method. In this study, the addition of calcined pyrite to the S system (SCP) accelerated electron generation and intra/extracellular transfer efficiency, thereby improving ACE and denitrification performance. The highest nitrate removal rate reached to 3.55 ± 0.01 mg N/L/h in SCP system, and the ACE was 103 % higher than that in S system. More importantly, calcined pyrite enhanced the enrichment of functional bacteria (Burkholderiales, Thiomonas and Sulfurovum) and functional genes which related to sulfur metabolism and electron transfer. This study was more effective in removing nitrate from groundwater without compromising the water quality.

Rapid start-up sulfur-driven autotrophic denitrification granular process: Extracellular electron transfer pathways and microbial community evolution.

Sulfur-driven autotrophic denitrification (SAD) granular process has significant advantages in treating low-carbon/nitrogen wastewater; however, the slow growth rate of sulfur-oxidizing bacteria (SOB) results in a prolonged start-up duration. In this study, the thiosulfate-driven autotrophic denitrification (TAD) was successfully initiated by inoculating anaerobic granular sludge on Day 7. Additionally, the electron donor was successfully transferred to the cheaper elemental sulfur from Day 32 to Day 54 at the nitrogen loading rate of 176.2 g N m-3 d-1. During long term experiment, the granules maintained compact structures with the α-helix/(ß-sheet + random coil) of 29.5-40.1 %. Extracellular electron transfer (EET) pathway shifted from indirect to direct when electron donors were switched thiosulfate to elemental sulfur. Microbial analysis suggested that thiosulfate improved EET involving enzymes activity. Thiobacillus and Sulfurimonas were dominant in TAD, whereas Longilinea was enriched in elemental sulfur-driven autotrophic denitrification. Overall, this strategy achieved in-situ enrichment of SOB in granules, thereby shortening start-up process.

Ultrafine CuO/graphene oxide cellulose nanocomposites with complementary framework for polycyclic aromatic hydrocarbon pollutants removal.

Efficient and sustainable methods for eliminating polycyclic aromatic hydrocarbon pollutants (PAHPs) are in highly desired. Proven technologies involve physical and chemical reactions that absorb PAHPs, however they encounter formidable challenges. Here, a bottom-up refining-grain strategy is proposed to rationally design ultrafine CuO/graphene oxide-cellulose nanocomposites (LCelCCu) with a mirror-like for tetracycline (TC) to substantially improve the efficient of the purification process by active integrated-sorption. The LCelCCu captures TC with a higher affinity and lower energy demand, as determined by sorption kinetic, isotherms, thermodynamics, and infrared and X-ray Photoelectron Spectroscopy. The resulting material could achieve ultra-high sorption capacity (2775.23 mg/g), kinetic (1.2499 L g-1 h-1) and high selectivity (up to 99.9 %) for TC, nearly surpassing all recent adsorbents. This study simultaneously unveils the pioneering role of simultaneous multi-site match sorption and subsequent advanced oxidation synergistically, fundamentally enhancing understanding of the structure-activity-selectivity relationship and inspires more sustainable water purification applications and broader material design considerations.

Inhibition of zinc ions in sulfur-driven autotrophic denitrification process: What is the behavior of extracellular polymeric substances?

Sulfur-driven autotrophic denitrification (SAD) process is a cost-effective and sustainable method for nitrogen removal from wastewater. However, a higher concentration of zinc ions (Zn(II)) flowing into wastewater treatment plants poses a potential threat to the SAD process. This study examined that a half maximal inhibitory concentration (IC50) of Zn(II) was 7 mg·L-1 in the SAD process. Additionally, the addition of 20 mg·L-1 Zn(II) resulted in a severe accumulation of nitrite to 150.20 ± 6.00 mg·L-1 when the initial concentration of nitrate was 500 mg·L-1. Moreover, the activities of nitrate reductase, nitrite reductase, dehydrogenase and electron transport system were significantly inhibited under Zn(II) stress. The addition of Zn(II) inhibited EPS secretion and worsened electrochemical properties. The result was attributed to the spontaneous binding between EPS and Zn(II), with a ΔG of -17.50 KJ·mol-1 and a binding constant of 1.77 × 104 M-1, respectively. Meanwhile, the protein, fulvic acid, and humic-like substances occurred static quenching after Zn(II) addition, with -OH and -C=O groups providing binding sites. The binding sequence was fulvic acid→protein→humic acid and -OH â†’ -C=O. Zn(II) also reduced the content of α-helix, which was unfavorable for electron transfer. Additionally, the Zn(II) loosened protein structure, resulting in a 50 % decrease in α-helix/(ß-sheet+random coil). This study reveals the effect of Zn(II) on the SAD process and enhances our understanding of EPS behavior under metal ions stress.

Meta-analyzing the mechanism of pyrogenic biochar strengthens nitrogen removal performance in sulfur-driven autotrophic denitrification system: Evidence from metatranscriptomics.

Sulfur-driven autotrophic denitrification (SAD) exhibits significant benefits in treating low carbon/nitrogen wastewater. This study presents an eco-friendly, cost-effective, and highly efficient method for enhancing nitrogen removal performance. The addition of biochar prepared at 300 °C (BC300) notably increased nitrogen removal efficiency by 31.60 %. BC300 concurrently enhanced electron production, the activities of the electron transfer system, and electron acceptors. With BC300, the ratio of NADH/NAD+ rose 2.00±0.11 times compared to without biochar, and the expression of NAD(P)H dehydrogenase genes was markedly up-regulated. In the electron transfer system, BC300 improved the electroactivity of extracellular polymeric substances and the activities of NADH dehydrogenase and complex III in intracellular electron transfer. Subsequently, electrons were directed into denitrification enzymes, where the nar, nir, nor, and nos related genes were highly expressed with BC300 addition. Significantly, BC300 activated the Clp and quorum sensing systems, positively influencing numerous gene expressions and microbial communication. Furthermore, the O%, H%, molar O/C, and aromaticity index in biochar were identified as crucial bioavailable parameters for enhancing nitrogen removal in the SAD process. This study not only confirms the application potential of biochar in SAD, but also advances our comprehension of its underlying mechanisms.

Membrane fouling mechanisms in the presence of microplastics and organic matter: The unexpected mitigating role of Ca2.

Ultrafiltration (UF) is demonstrated to be highly effective in the removal of microplastics (MPs), but the presence of coexisting foulants introduces significant uncertainties into the associated membrane fouling behaviors. In this study, membrane fouling mechanisms were investigated when MPs, represented by polystyrene (PS), coexisted with typical organic foulants (sodium alginate, SA) and inorganic ions (Ca2+). Fouling tests revealed that the order of Ca2+ addition significantly impacted the fouling behavior of the SA-PS combined foulants. Specifically, the specific filtration resistance (SFR) was reduced by 40.82 % in the SA-PS-Ca2+ foulants and by 90.92 % in the SA-Ca2+-PS foulants, compared to the SA-PS foulants. X-ray photoelectron spectroscopy and density functional theory calculations indicated that sufficient cross-linking of Ca2+ with SA molecular chains in the SA-Ca2+-PS foulants, forming a large-scale 3D network that encapsulated more PS particles and resulted in larger flocs than those found in the SA-PS-Ca2+ foulants. According to extended Flory-Huggins theory, the improved filtration performance of the SA-PS combined foulants was due to substantial changes in chemical potential during their transition from gel to flocs upon Ca2+ addition. Furthermore, interfacial thermodynamic analyses suggested that increased repulsion between SA-Ca2+-PS foulants and between them and the membrane led to a looser fouling layer, significantly mitigating membrane fouling. This study elucidates the fouling mechanisms in the presence of MPs and other foulants from the perspectives of energy changes and molecular structures, providing novel insights for developing strategies to mitigate membrane fouling.

Analysis of aerobic granular sludge formation based on grey system theory.

Based on grey entropy analysis, the relational grade of operational parameters with aerobic granular sludge's granulation indicators was studied. The former consisted of settling time (ST), aeration time (AT), superficial gas velocity (SGV), height/diameter (H/D) ratio and organic loading rates (OLR), the latter included sludge volume index (SVI) and set-up time. The calculated result showed that for SVI and set-up time, the influence orders and the corresponding grey entropy relational grades (GERG) were: SGV (0.9935) > AT (0.9921) > OLR (0.9894) > ST (0.9876) > H/D (0.9857) and SGV (0.9928) > H/D (0.9914) > AT (0.9909) > OLR (0.9897) > ST (0.9878). The chosen parameters were all key impact factors as each GERG was larger than 0.98. SGV played an important role in improving SVI transformation and facilitating the set-up process. The influence of ST on SVI and set-up time was relatively low due to its dual functions. SVI transformation and rapid set-up demanded different optimal H/D ratio scopes (10-20 and 16-20). Meanwhile, different functions could be obtained through adjusting certain factors' scope.

The collaborative incentive effect in adsorption-photocatalysis: A special perspective on phosphorus recovery and reuse.

Achieving efficient recovery and direct utilization of phosphorus as one of the important components of the green economy is a huge challenge. Herein, we innovatively constructed a coupling adsorption-photocatalytic (CAP) process using synthetic dual-functional Mg-modified carbon nitride (CN-MgO). The CAP could utilize the recovered phosphorus from wastewater to promote the in-situ degradation of refractory organic pollutants via CN-MgO, where its phosphorus adsorption capacity and photocatalytic activity were significantly and synergistically increased. It was specifically reflected in the high phosphorus adsorption capacity of CN-MgO (218 mg/g), which was 153.5 times that of carbon nitride (1.42 mg/g), and its theoretical maximum adsorption capacity could reach 332 mg P/g. Subsequently, the phosphorus-enriched sample (CN-MgO-P) was employed as a photocatalyst to remove tetracycline with a reaction rate (k = 0.07177 min-1) 2.33 times higher than that of carbon nitride (k = 0.0327 min-1). Notably, the coordinated incentive mechanism present in this CAP between adsorption and photocatalysis may be attributed to the more adsorption sites of CN-MgO and the facilitation of hydroxyl production through adsorbed phosphorus, which ensured the feasibility of creating environmental value from the phosphorus in wastewater by means of CAP. This study provides a new perspective on the recovery and reuse of phosphorus resources in wastewater and the integration of environmental technologies in multiple fields.

Achieving nitrogen removal with low material and energy consumption through partial nitrification coupled with short-cut sulfur autotrophic denitrification in a single-stage SBR.

An innovative partial nitrification and short-cut sulfur autotrophic denitrification (PN-SSAD, NH4+-N â†’ NO2--N â†’ N2) coupled system in a single-stage SBR was proposed to treat low C/N wastewater with low material and energy consumption. Nearly 50 % alkalinity consumption and 40 % sulfate production were reduced in S0-SSAD compared with S0-SAD, whereas the autotrophic denitrification rate was increased by 65 %. In S0-PN-SSAD, the TN removal efficiency reached almost 99 % without additional organic carbon. Furthermore, pyrite (FeS2) rather than S0 served as the electron donor to optimize the PN-SSAD process. The practical sulfate production in S0-PN-SSAD and FeS2-PN-SSAD were about 38 % and 52 % lower than complete nitrification and sulfur autotrophic denitrification (CN-SAD), respectively. Thiobacillus was the major autotrophic denitrification bacteria in S0-PN-SSAD (34.47 %) and FeS2-PN-SSAD (14.88 %). Nitrosomonas and Thiobacillus played a synergistic effect in the coupled system. FeS2-PN-SSAD is expected as an alternative technology for nitrification and heterotrophic denitrification (HD) in treating low C/N wastewater.

Solar-enhanced bio-electro-Fenton driven by sediment microbial fuel cell for ametryn degradation in simulated seawater.

In marine aquaculture areas, herbicides have been used to inhibit the wild growth of seaweed, which may seriously affect the ecological environment and food safety. Here the commonly applied ametryn was used as the representative pollutant, and solar enhanced bio-electro-Fenton driven in situ by sediment microbial fuel cell (SMFC) was proposed to degrade ametryn in simulated seawater. SMFC with γ-FeOOH-coated carbon felt cathode was operated under the simulated solar light (γ-FeOOH-SMFC), where two-electron oxygen reduction and activation of H2O2 occurred to promote the production of hydroxyl radicals at the cathode. Hydroxyl radicals, photo-generated holes, and anodic microorganism worked together to degrade ametryn with an initial concentration of 2 mg/L in the self-driven system. The removal efficiency of ametryn in γ-FeOOH-SMFC was 98.7 % during the operation period of 49 days, which was 6 times higher than that under natural degradation condition. When γ-FeOOH-SMFC was in the steady phase, oxidative species were continuously and efficiently generated. The maximum power density (Pmax) of γ-FeOOH-SMFC was 44.6 W/m3. According to the intermediate products of ametryn degradation in γ-FeOOH-SMFC, four possible pathways of ametryn degradation were proposed. This study provides an effective, cost-saving, and in situ treatment for refractory organics in seawater.

Photocatalytic hydrogel film assisted forward osmosis (PFO) for water treatment: Sustainable performance and contaminant control.

The integration of catalytic oxidation with forward osmosis (FO) holds promising potential to address two crucial challenges encountered by FO: fouling and unsustainable performance, but suitable approaches are still rare. Herein, we have successfully developed a photocatalysis-assisted forward osmosis (PFO) system. In the PFO, a self-made porous carbon nitride doped functional carbon nanotube photocatalytic hydrogel film (PCN@CNTM) was engaged in the FO process in an inventive way by simply sticking to the commercial FO membrane surface, preventing damage to the membrane from the catalyst's direct insertion and delaying the assault from the oxidation groups. PFO allowed organic pollutants to decompose in the feed solution (90%) and on the membrane surface, regulating the water chemical potential and giving the FO membrane antifouling properties. This resulted in sustainable water flux (11.8 LMH) with no significant membrane fouling in PFO, whereas in FO alone there was a significant fouling and flux drop (from 12.73 to 7.23 LMH in 4 h). Moreover, the expensive FO membrane was protected while the hydrogel film can be replaced on demand. The PFO exemplifies the concept of synergistic technology integration, presenting a new perspective on harnessing the strengths of distinct technologies in a mutually beneficial manner.

A unified thermodynamic fouling mechanism based on forward osmosis membrane unique properties: An asymmetric structure and reverse solute diffusion.

Fouling mechanism of the forward osmosis membrane, which was peculiarly featured by the asymmetric membrane structure and reverse solute diffusion, was investigated at the molecular level and from the energy perspective. Two noteworthy fouling behaviors were observed in batch fouling tests conducted in AL-FS mode (active layer facing feed solution) and AL-DS mode (active layer facing draw solution) after filtering foulants with identical volume: 1) after filtering 100 mL of foulants, the flux decline rate in AL-DS mode was 1.78 times faster than that in AL-FS mode, but the flux decline behaviors of the two modes were similar in the subsequent filtration stages; 2) although the foulant layer weight of the same mode increased linearly in middle and late stages, the flux loss rate was distinctly different. Thermodynamic analysis indicated that the attractive interaction energy between the foulants and the support layer was about 5 times higher than that between the foulants and the active layer, well interpreting the higher flux decline rate of AL-DS mode in initial stage. Meanwhile, a non-invasive microscope observed that the structure of the fouling layer remarkably changed from loose to dense in the middle stage, and stabilized in the late stage. Furthermore, quantum chemistry calculation proved that the reverse diffusion of NaCl brought alginate molecular chains closer, whereas the distance between them tended to be constant as the continuous increase of NaCl. Based on these findings, the thermodynamic fouling mechanism proposed by combining the structure change process of the fouling layer with Flory-Huggins lattice theory satisfactorily interpreted the noteworthy fouling behaviors caused by reverse NaCl diffusion in middle and late stages. The revealed fouling mechanism unifies the adhesion and filtration behaviors related to the unique properties of FO membrane, deepening understanding of membrane fouling in the dynamic and complex ternary system of the FO process.

Mutual effects of CO2 absorption and H2-mediated electromethanogenesis triggering efficient biogas upgrading.

Anaerobic digestion coupled with bioelectrochemical system (BES) is a promising approach for biogas upgrading with low energy input. However, the alkalinity generation from electromethanogenesis is invariably ignored which could serve as a potential assistant for CO2 removal through the transformation into dissolved inorganic carbon (DIC). Herein, a novel bioelectrochemical CO2 conversion in the methanogenic BES was proposed based on active CO2 capture and in-situ microbial utilization. It was found that the BES using a stainless steel/carbon felt hybrid biocathode (BES-SSCF reactor) achieved a CH4 yield of 0.33 ± 0.03 LCH4/gCODremoval and increased CH4 production rate by 28.3% of BES-CF reactor at 1.0 V applied voltage. As the experiment progressed, CH4 content increased to 93.1% and CO2 content in the upgraded biogas maintained at below 3%. The continuous proton consumption from H2 evolution reaction in the hybrid biocathode was capable of creating a slightly alkaline condition in the BES-SSCF reactor and thereby the CO2 capture as bicarbonate was enhanced through endogenous alkalinity absorption. Microbial community analysis revealed that significant enrichment of Methanobacterium and Methanosarcina at the BES-SSCF cathodic biofilm was favorable for bicarbonate reduction into CH4 via establishment of H2-mediated electron transfer. Consequently, the remained CO2 and DIC only accounted for 12% of total carbon in the BES-SSCF reactor and the high conversion rate of CO2 to CH4 (82.3%) was achieved. These results unraveled an innovative CO2 utilization mechanism integrating CO2 absorption with H2-mediated electromethanogenesis.

Fundamental thermodynamic mechanisms of membrane fouling caused by transparent exopolymer particles (TEP) in water treatment.

While transparent exopolymer particles (TEP) has high fouling potential, its underlying fouling mechanisms have not yet been well revealed. In current work, fouling characteristics of TEP under different Ca2+ concentrations (0 to 1.5 mM) were investigated. TEP quantification and filtration tests showed that TEP contents increased with Ca2+ concentration, while TEP's specific filtration resistance (SFR) under the influence of Ca2+ concentration presented a unimodal pattern. The peak of TEP's SFR reached at Ca2+ concentration of 1 mM when SA concentration was 0.3 g·L-1. A series of characterizations suggested that microstructure transformation of TEP particles was the main contributor to the resistance variations of TEP solution. The optical microscope observation showed that above and below the critical Ca2+ concentration (1 mM when SA concentration is 0.3 g·L-1 in this study), the formed TEP existed in the form of c-TEP (average particle size is 0.24 µm) and p-TEP (average particle size is 1.05 µm), respectively. Thermodynamic analysis showed that the adhesion ability of c-TEP (-249,989 and - 303,692 kT) was more than 19 times than that of p-TEP (-12,905 kT), which would accelerate foulant layer formation. In addition, below the critical value, the increased SFR with Ca2+ concentration could be explained by integrating Flory-Huggins lattice theory with the preferential intermolecular coordination. Above the critical value, the decreased SFR can be attributed to the formation of a "large-size crack structure" cake layer from the p-TEP. This study revealed fundamental mechanisms of membrane fouling caused by TEP, greatly deepening understanding of TEP fouling, and facilitating to development of effective fouling control strategies.

Molecular-level insights into the mitigation of magnesium-natural organic matter induced ultrafiltration membrane fouling by high-dose calcium based on DFT calculation.

While magnesium cation (Mg2+) universally coexists with natural organic matter (NOM) in the water environment, influence of Mg2+ on NOM fouling in membrane filtration process is still unclear. This work was therefore performed to investigate effects of Mg2+ on NOM (sodium alginate (SA) as a model substance) fouling and role of Ca2+ in mitigating fouling from Mg2+ in the ultrafiltration (UF) water treatment process. Filtration tests showed two interesting fouling phenomena: (1) membrane fouling caused by combination of Mg2+ and SA maintained at a high value with the increased Mg2+ concentration; (2) the high fouling property of Mg2+ can be significantly improved by the prominent addition of calcium cation (Ca2+). It was found that changes of foulant morphology played essential roles through thermodynamic mechanisms represented by the Flory-Huggins lattice theory. Density functional theory (DFT) calculation showed that the combination of SA and Mg2+ tends to coordinate two terminal carboxyl groups in SA, beneficial to stretching alginate chains and forming a stable gel network at low doses. In addition, intramolecular coordination is difficult to occur between SA and Mg2+ due to the high hydration repulsion radius of Mg2+. Therefore, a dense and thick gel network remained even under high Mg2+concentration. Furthermore, due to the higher binding affinity of Ca2+ over Mg2+, high doses of Ca2+ trigger a transition of the stable SA-Mg2+ gel network to other configurations where flocculation and aggregation occur, thereby reducing the specific filtration resistance. The proposed thermodynamic mechanism satisfactorily explained the above interesting fouling behaviors, facilitating to development of new solutions to control membrane fouling.