Adsorptive performance and mechanism exploration of l-lysine functionalized celluloses for enhanced removal of Pb(II) from aqueous medium.

In this study, two novel biosorbents of l-lysine grafted cellulose (L-PCM, L-TCF) were prepared for Pb(II) removal from aqueous solutions. Various adsorption parameters were surveyed, such as adsorbent dosages, initial concentration of Pb(II), temperature and pH, using adsorption techniques. At normal temperature, less adsorbent can achieve better adsorption capacity (89.71 ± 0.27 mg g-1 with 0.5 g L-1 of L-PCM, 16.84 ± 0.02 mg g-1 with 3.0 g L-1 of L-TCF). The pH range of application for L-PCM was 4-12 and that of L-TCF was 4-13. The adsorption of Pb(II) by biosorbents went through the boundary layer diffusion stage and void diffusion stage. The adsorption mechanism was chemisorption based on multilayer heterogeneous adsorption. The pseudo-second-order model fitted the adsorption kinetics perfectly. The Freundlich isotherm model adequately described Multimolecular equilibrium relationship between Pb(II) and biosorbents; the predicted maximum adsorption capacities of the two adsorbents were 904.12 and 46.74 mg g-1, respectively. The results showed that the adsorption mechanism was the electrostatic attraction between Pb(II) and -COOH and the complexation between Pb(II) and -NH2. This work demonstrated that l-lysine modified cellulose-based biosorbents have great potential in the field of Pb(II) removal from aqueous solutions.

Microbially mediated Fe-N coupled cycling at different hydrological regimes in riparian wetland.

Although the significance of the coupled Fe- and N- cycling processes on biogeochemical transformation in riparian wetlands is well-known, the regulation associated with the changes on the microbiotas during different hydrological regimes remains unclear. This study performed field investigations on the bacterial community compositions (BCC) and specific genera associated to Fe- and N- cycling in the rhizosphere soil and sediments in a riparian wetland in Poyang lake, China. The predominant phyla Proteobacteria, Acidobacteria, and Nitrospirae from all the samples remarkably decreased after long-term continuous flooding, while Actinobacteria, Firmicutes and Bacteroidetes were enriched. For the family level, the relative abundances of iron-oxidizing bacteria (FeOB) Gallionellaceae, and N fixing bacteria Nitrospiraceae and Bradyrhizobiaceae significantly declined upon the long-term flooding and then increased with dewatering, which were consistent with the functional genes sequencing analysis. In which, the Bradyrhizobiaceae (RA 2.0 %-34.6 %) was the dominant nirS denitrifier and potential iron-reducing bacteria (FeRB), Sideroxydans lithotrophicus was one of the dominant FeOB (RA 1.7 %-23 %), which was also identified to be the nirS dentrifier (RA 0.2 %-4.3 %). The absolute quantification of the functional genes levels including nirS, nirK, FeRB (Geobacter spp.) showed their significant increases by 3-7 times upon desiccation compared to that under post-CF. The PCA and RDA results indicated the linkage between redox changes of N and Fe during inundation mediated by FeRB, NOB, and FeOB, which were closely related to hydrochemical indices NO3-, Fe2+ and SO42-. These evidences all implied the likely occurrence of nitrate reduction coupled to Fe(II) oxidation (NRFeOx) under oligotrophic conditions, which was potentially facilitated by metabolizers consisting of highly correlated Bradyrhizobiaceae and Sideroxydans (rho = 0.86, p < 0.01). These findings provide an interpretation of the biological reactions in the microbially mediated NRFeOx processes driven by hydrological change, which could assist the mechanistic understanding of the global biogeochemical cycles of iron and nitrogen in riparian wetlands.

EDTA-Na2 as a recoverable draw solute for water extraction in forward osmosis.

Regeneration and reuse of draw solute (DS) is a key challenge in the application of forward osmosis (FO) technologies. Herein, EDTA-Na2 was studied as a recoverable DS for water extraction by taking advantages of its pH-responsive property. The FO system using EDTA DS achieved a higher water flux of 2.22 ± 0.06 L m-2 h-1 and a significantly lower reverse salt flux (RSF) of 0.06 ± 0.01 g m-2 h-1, compared to that with NaCl DS having either the same DS concentration or the same Na+ concentration. The suitable pH range for the application of EDTA DS was between 4.0 and 10.5. A simple recovery method via combined pH adjustment and microfiltration was employed to recover EDTA DS and could achieve the recovery efficiency (at pH 2) of 96.26 ± 0.48%, 97.13 ± 1.03% and 98.56 ± 1.40% by using H2SO4, H3PO4 and HCl, respectively. The lowest acid cost for DS recovery was estimated from 0.0012 ± 0.0001 to 0.0162 ± 0.0003 $ g-1 by using H2SO4. The recovered EDTA DS could be reused in the subsequent FO operation and the overall recovery efficiency was 94.4% for four reuse cycles. These results have demonstrated the feasible of EDTA-Na2 DS and a potentially cost-effective recovery approach, and encouraged further exploration of using EDTA-based compounds as a draw solute for FO applications.

Organic carbon determines nitrous oxide consumption activity of clade I and II nosZ bacteria: Genomic and biokinetic insights.

Harnessing nitrous oxide (N2O)-reducing bacteria is a promising strategy to reduce the N2O footprint of engineered systems. Applying a preferred organic carbon source as an electron donor accelerates N2O consumption by these bacteria. However, their N2O consumption potential and activity when fed different organic carbon species remain unclear. Here, we systematically compared the effects of various organic carbon sources on the activity of N2O-reducing bacteria via investigation of their biokinetic properties and genomic potentials. Five organic carbon sources-acetate, succinate, glycerol, ethanol, and methanol-were fed to four N2O-reducing bacteria harboring either clade I or clade II nosZ gene. Respirometric analyses were performed with four N2O-reducing bacterial strains, identifying distinct shifts in DO- and N2O-consumption biokinetics in response to the different feeding schemes. Regardless of the N2O-reducing bacteria, higher N2O consumption rates, accompanied by higher biomass yields, were obtained with acetate and succinate. The biomass yield (15.45 ± 1.07 mg-biomass mmol-N2O-1) of Azospira sp. strain I13 (clade II nosZ) observed under acetate-fed condition was significantly higher than those of Paracoccus denitrificans and Pseudomonas stutzeri, exhibiting greater metabolic efficiency. However, the spectrum of the organic carbon species utilizable to Azospira sp. strain I13 was limited, as demonstrated by the highly variable N2O consumption rates observed with different substrates. The potential to metabolize the supplemented carbon sources was investigated by genomic analysis, the results of which corroborated the N2O consumption biokinetics results. Moreover, electron donor selection had a substantial impact on how N2O consumption activities were recovered after oxygen exposure. Collectively, our findings highlight the importance of choosing appropriate electron donor additives for increasing the N2O sink capability of biological nitrogen removal systems.

The response mechanism of Hydrilla verticillata and leaf epiphytic biofilms to depth and nutrient removal.

The mechanism of morphological and physiological regulation of submerged aquatic plants (Hydrilla verticillata) is influenced by spatial and environmental changes related to water depth gradients. In the present study, changes in the aquatic microcosm were explored at the depth gradients of 0.3 m, 0.6 m, 0.9 m, 1.2 m, and 1.5 m, and the depth was recognized as a critical factor for improving water quality, especially for the removal of total phosphorus (TP) and recalcitrant protein-like molecules. At 0.9 m, the removal rates of TP and protein-like substances reached 78% and 18.67%, respectively, 1.76 times and 1.28 times the rates at 0.3 m. The maximum shoot/root growth and chlorophyll (a + b) suggest photosynthesis inhibition is minimal at 1.2 m. Fluctuations in enzyme activities imply an antioxidant response to lipid peroxidation damage under different oxidative stress. The adjusted activities of glutamine synthetase (GS) and alkaline phosphatase (APA) were an adaptive nutrient utilization strategy to different water depths. Microbiological diversity analysis of biofilms indicates that community structure changes in response to water depth. Considering the growth status and nutrient removal effects, the results indicate that the optimal planting depth for H. verticillata is 0.9-1.2 m. These findings contribute to understanding water purification mechanisms in depth gradients, and support the effective rebuilding and management of submerged macrophyte communities in natural shallow lakes.

Novel green chitosan-pectin gel beads for the removal of Cu(II), Cd(II), Hg(II) and Pb(II) from aqueous solution.

Chitosan-pectin gel beads (CPBs) were synthesized via a facile and green method and applied to remove heavy metals from aqueous solution. The structural characteristics of CPBs were investigated by SEM and FTIR, the mechanical strength of CPBs was measured by Texture Analyzer and the stability of CPBs was evaluated in acidic solution. To study the adsorption characteristics, the effect of pH, contact time, initial heavy metals concentration, temperature, adsorption mechanism and regeneration were systematically investigated. The adsorption kinetics fitted well pseudo-second-order model, and the adsorption isotherms were well described by Langmuir model. The maximum adsorption capacities of Cu(II), Cd(II), Hg(II) and Pb(II) were 169.4, 177.6, 208.5 and 266.5 mg/g, respectively. The adsorption-desorption experiments revealed that the CPBs exhibited a great reusability. Thus, the synthesized CPBs in this study had the potential to be utilized as an environment-friendly and green adsorbent for the removal of heavy metals.

Mechanism analysis for the process-dependent driven mode of NaHCO3 in algal antibiotic removal: efficiency, degradation pathway and metabolic response.

This work provided a comprehensive perspective to investigate the performance of NaHCO3-driving effect and mechanism including the antibiotic removal, degradation pathway and metabolites analysis, and the algal physiological response during the removal process. Cefuroxime sodium was selected as the target antibiotic. Our results showed that NaHCO3 did not facilitate self-decomposition of the target antibiotic, while drove the improvement on the removal capacity of every algal cell, which then attributed to the total removal efficiency. After 24 h, there was an improvement on the removal rate of the target antibiotic (from 10.21% to 92.89%) when NaHCO3 was added. The degradation pathway of the target antibiotic was confirmed by the formation of three main products (M1, M2 and M3), and the degradation process, that from M1 to M2 and M2 to M3, was accelerated by the existence of NaHCO3. Besides, a 4-stage model illustrated the relationship between NaHCO3 and antibiotic removal process. Moreover, algal culture that supplemented with NaHCO3 demonstrated a better growth capacity. A large increase in the content of chlorophyll a and a moderate increase in the activity of two carbon metabolic enzymes (RuBisCO and CA) might be viewed as a positive response of the algae during the NaHCO3-driving process.

Identification and evaluation of suitable reference genes for gene expression analysis in rubber tree leaf.

Gene expression profiles are increasingly applied to investigate molecular mechanism for which, normalization with suitable reference genes is critical. Previously we have reported several suitable reference genes for laticifer samples from rubber tree, however, little is known in leaf. The main objective of this current study was to identify some stable expression reference genes at various developmental stages of leaf, as well as during abiotic (high and low temperature extremes) and biotic stresses (pathogen stress). Gene expression profilings identified the ubiquitin-proteasome system as excellent potential as reference genes for rubber tree leaf. Among a total of 30 tested genes investigated, 24 new candidate (including 11 genes involved in the ubiquitin-proteasome system), 4 previously identified and 2 specific genes, were further evaluated using quantitative real-time PCR. Our results indicated that the new candidate genes had better expression stability comparing with others. For instance, an ubiquitin conjugating enzyme (RG0099) and three ubiquitin-protein ligases (RG0928, RG2190 and RG0118) expressed stably in all samples, and were confirmed to be suitable reference genes for rubber tree leaf under four different conditions. Finally, we suggest that using more than one reference gene may be appropriate in gene expression studies when employing different software to normalize gene expression data. Our findings have significant implications for the reliability of data obtained from genomics studies in rubber tree and perhaps in other species.

Fabrication of a Novel Bifunctional Nanocomposite with Improved Selectivity for Simultaneous Nitrate and Phosphate Removal from Water.

Phosphorus and nitrogen compounds are both the main sources of eutrophication and coexist in some municipal effluents or eutrophic waters; elimination of phosphorus and nitrogen from wastewater is becoming an imperative but also a hard task. Herein, an innovative bifunctional nanocomposite HFO@TPR was developed for synchronous nitrate/phosphate elimination from water. A macroporous polystyrene microspheres modified with triethylamine functional groups was synthesized as the host of HFO@TPR for selective nitrate removal, and Fe(III) hydroxide (HFO) nanoparticles were implanted inside as the active species for specific phosphate removal. Compared to other commercial adsorbents, HFO@TPR exhibited outstanding selectivity and preference toward nitrates and phosphates, and the coexisting anions exert an insignificant effect on adsorption performance. Such exceptional bifuntionality of HFO@TPR was achieved through two pathways, that is, nitrate was preferentially adsorbed by the fixed triethylamine groups through the electrostatic attraction, and phosphate was preferentially captured by the encapsulated HFO nanoparticles through the inner-sphere complexation. The exhausted HFO@TPR could be effectively regenerated by using a NaOH-NaCl mixed reagent for cyclic use with a relative constant efficiency. In addition, column adsorption experiments demonstrated that HFO@TPR could eliminate nitrate from 18 to <10 mg N/L with the treatment capacity of ∼600 bed volume (BV), and meanwhile remove phosphate from 2.5 to <0.2 mg P/L with the treatment capacity of ∼750 BV. We believe what we found in this study could advance the method on how to develop bifunctional adsorbents for synchronous removal of coexisting contaminants from water.

Integrated toxic evaluation of sulfamethazine on zebrafish: Including two lifespan stages (embryo-larval and adult) and three exposure periods (exposure, post-exposure and re-exposure).

Persistence of antibiotics in aquatic environment may pose a risk to the non-target aquatic organisms. This study provided an integrated evaluation to analyze the toxic stress of sulfamethazine (SMZ) on zebrafish in two lifespan stages (embryo-larval and adult) and three exposure periods (exposure, post-exposure and re-exposure). Zebrafish embryos and adult zebrafish were exposed to SMZ at 0.2, 20 and 2000 µg/L, respectively. The results showed that SMZ at any given concentration inhibited the hatching of embryos at 58-96 hpf (hours post-fertilization). Our result also indicated that two major kinds of the malformation, which was induced by the antibiotic, were edema and spinal curvature. Additionally, the antibiotic stimulated the heartbeat while reduced the body length of the embryo at 72 hpf. Superoxide dismutase (SOD) activities and malondialdehyde (MDA) contents significantly increased at 120 hpf when the embryos were exposed to the lowest concentration (0.2 µg/L) of the antibiotic. On the other hand, the antibiotic induced SOD activities and MDA contents in adult zebrafish in the exposure and re-exposure periods. The MDA contents could recover while SOD activities still increased in 2 d after the exposure. Both SOD activities and MDA contents could recover in 7 d after the exposure. Levels of SOD and MDA in the re-exposure were higher than those in the first exposure. Our results suggested that SMZ had toxic effects on both embryos and adult zebrafish, and provided an integrated evaluation of the toxic effects of SMZ on zebrafish at a new perspective.

Electrosorption enhanced electrooxidation of a model organic pollutant at 3D SnO2-Sb electrode in superimposed pulse current mode.

In this work, the novel pulse "electrosorption-electrooxidation-electrosorption" (PESO) mode is developed in the superimposed pulse current system for benzoic acid oxidation. Due to the synergistic effect of electrosorption and electrooxidation at TiO2-NTs/3D-SnO2-Sb electrode in PESO mode, the enhancement of removal efficiency, improvement in mass transport and decrease of energy consumption were significantly obvious. The mechanism for the great enhancement of the mode is analyzed in details. The strengthened interaction between electrode and organics, increased instantaneous currents and lower intermediate accumulation contributed to the significant enhancement of electrochemical performance of the superimposed pulse system. The pulse PESO mode was an efficient and promising method for treating organic pollutants.

[Stability of C60 nanoparticles in aquatic systems].

The influences of storage time, pH, electrolytes and organic matters on the stability of two different suspensions of C60 nanoparticles were investigated. The results showed that the C60 nanoparticles prepared by solvent substitution (C60/son) were more stable than that prepared by prolonged stirring (C60/aq), and kept stable for a period of time. Higher pH enhanced the stability of C60 nanoparticles. The presence of electrolyte made a dramatic decrease in the surface zeta potential and an increase in the particle size. The aggregation process of C60 nanoparticles exhibited slow and rapid regions, which was found to be consistent with the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory of colloidal stability. The critical coagulation concentration (CCC) values of C60/son, obtained from the intersection of the interpolated lines through the slow and fast regions, were estimated as 321 mmol x L(-1) NaCl, 316 mmol x L(-1) KCl, 9.6 mmol x L(-1) MgCl2 and 6.7 mmol x L(-1) CaCl2. The CCC values of C60/aq were estimated as 295 mmol x L(-1) NaCl, 278 mmol x L(-1) KCl, 7.8 mmol x L(-1) MgCl2 and 5.9 mmol x L(-1) CaCl2, which were much higher than their concentrations in natural waters. The presence of humic acid enhanced the stability of C60 nanoparticles, which was attributable to steric repulsion. Therefore, C60 nanoparticles will keep relatively stable in typical aquatic environments.

Photolysis kinetics and influencing factors of bisphenol S in aqueous solutions.

The photodegradation of bisphenol S (BPS) in aqueous solutions was studied under different conditions. Photolysis and kinetics were investigated, as were the photolysis mechanism and the influences of initial pH value, light source, and environmental substances in water. The results showed that the photolysis of BPS occurred under UV light, and the rate increased with light source intensity. The photolysis of 5.0-50.0 mg/L BPS in water followed first-order kinetics: the rate was gamma = 0.0161C(BPS) under a 40-W UV-lamp, and the degradation half-life was 43.1 min. Due to its absorption of light, direct photolysis of BPS was a predominant pathway for BPS but was not obviously affected by reactive oxygen species. The results confirmed that the photolysis rates of BPS in alkaline water solution were faster than those in acidic and neutral water solution because of the ionization of BPS. The photodegradation rate of BPS increased in the presence of chloride and ferric ions, while the rate was inhibited by nitrate and phosphate in aqueous solution.

Influence of diatomite addition on membrane fouling and performance in a submerged membrane bioreactor.

This paper examined the effect of diatomite addition on membrane fouling and process performance in an anoxic/oxic submerged membrane bioreactor (A/O MBR). Particle size distribution, molecular weight distribution and microbial activity have been investigated to characterize the sludge mixed liquor. Results show that diatomite addition is a reliable and effective approach in terms of both membrane fouling mitigation and pollutants removal improvement. The MBR system with diatomite addition of 50 mg/L enhanced the removal of COD, TN and TP by 0.9%, 6.9% and 31.2%, respectively, as compared to the control MBR (without diatomite addition). The NH(4)-N removal always maintained at a high level of over 98% irrespective of diatomite addition. Due to the hybrid effect of adsorption and co-precipitation on fine colloids and dissolved organic matter (DOM) from the addition of diatomite, a reduction in foulants amount, an increase in microbial floc size and an improvement in sludge settleability have been achieved simultaneously. As a result, the membrane fouling rate was mitigated successfully.

Simulation and assessment of sludge concentration and rheology in the process of waste activated sludge treatment.

The process of using flat-sheet membrane for simultaneous sludge thickening and digestion (MSTD) was employed. The variations of sludge concentration and rheology were characterized and simulated. Based on mass balance analysis, mathematical models were developed and successfully used to predict and evaluate the variations of sludge concentration and the digestion efficiency in the MSTD process. The apparent viscosity of sludge could be modeled as functions of mixed liquor suspended solids and shear rates. The sludge in the MSTD process showed both shear-thinning and viscoplastic behaviour, and under various shear rates different rheological models could be chosen to predict their flow behaviour. It was also found that sludge concentration and viscosity had significant correlations with membrane fouling in the MSTD process.

[Variations of biological stability and disinfection byproduct in water distribution systems and their correlations].

Variations of assimilable organic carbon (AOC), trihalomethanes (THMs) and haloacetic acids (HAAs) in two different water distribution systems (DSs) were investigated in Shanghai, a eastern city of China. Correlations of drinking water biological stability and disinfection byproduct were analyzed. The results show that AOC and HAAs are varied based on chlorine residual and microbial activity. And their concentrations are increased by chlorine oxidation in the front part of pipe networks where high residual chlorine contents exist, while reduced by bacterial consuming in the end part pipe networks where low residual chlorine exists. Changes of THMs in DSs are influenced by residual chlorine merely, and contents have risen with the extension of pipe net. There are evident linear relationships between HAAs and AOC, and precursors of them are homologous. Contents of THMs are positively correlated with AOC. Therefore biological stability and disinfection byproduct, as two important factors of drinking water safety, present inherent relevances.

Biopurification of industrial waste gas from rubber regeneration.

By using the biopurifying technology, the organic waste gas in low concentrations emitted from the rubber-regeneration process was purified in this research. The result of the 100-day continuous running test of the industrial test device indicated that the purification efficiency of toluene in the rubber-regeneration waste gas could be maintained at about 90% for a long period of time and the treated waste gas could meet the China National Emission Standard. The cost of waste gas biotreatment was about 0.12-0.14% of rubber-regeneration production value of the factory. The biopurifying technology of waste gas displayed its excellent technical advancement and economic rationale. The following industrialized device was run continuously and passed the examination and acceptance by the local EPA.