Coagulation performance and mechanism analysis of humic acid by using covalently bonded coagulants: effect of pH and matching mechanism of humic acid functional groups.

Conventional inorganic coagulants (Al, Fe) and Al/Fe-based covalently bonded flocculants (CAFMs) had different hydrolysis species at different pHs, which subsequently led to differences in their binding sites and complexation ability with humic acid (HA). Studying the binding sites and interactions between CAFMs, AlCl3 (Al), and FeCl3 (Fe) hydrolysates and HA molecules is critical to understanding the coagulation mechanism. The results found that CAFM 0.6, Al, and AlCl3 combined FeCl3 (Al/Fe) removed more than 90% of HA at pH 6, and CAFMs showed higher HA removal rate than that of Al, Fe, and Al/Fe under the same reaction conditions. The flocs of CAFMs contained abundant -NH2/OH as well as the large particle size, compact structure, and excellent settling performance. The hydrolyzed species of Al and Fe were predominantly Alb and Feb at pH 6, but the hydrolyzed species of CAFMs were primarily (Al + Fe)c. Moreover, the hydrolyzed species of Al and Al/Fe were found to complex with HA functional groups such as -COOH, C = O, C-H/C-C, C = C, and C-OH to form ligand bonds, while the hydrolyzed species (Al + Fe)c of CAFMs could deeply interact with HA functional groups including C-O, -COOH, C = O, C-H/C-C, C = C, and C-OH by the adsorption and sweeping.

Hydrochloric acid-modified fungi-microalgae biochar for adsorption of tetracycline hydrochloride: Performance and mechanism.

Novel biochar (BC) was prepared by pyrolysis using Aspergillus oryzae-Microcystis aeruginosa (AOMA) flocs as raw materials. It has been used for tetracycline hydrochloride (TC) adsorption along with acid (HBC) and alkali modification (OHBC). Compared with BC (114.5 m2 g-1) and OHBC (283.9 m2 g-1), HBC had a larger specific surface area (SBET = 338.6 m2 g-1). Meanwhile, the Elovich kinetic and Sip isotherm models adequately fit the adsorption data, and intraparticle diffusion is the controlling factor for TC adsorption diffusion on HBC. Furthermore, the thermodynamic data indicated that this adsorption was endothermic and spontaneous. The experimental results demonstrated that there are multiple interactions during the adsorption reaction process, including pore filling, H-bonds, π-π interaction, hydrophobic affinity, and van der Waals forces. In general, biochar prepared from flocs of AOMA can be used to remediate tetracycline-contaminated water, and it is of great significance in improving resource utilization.

Enhancement of 15% calcium oxide doped nano zero-valent iron on arsenic removal from high-arsenic acid wastewater.

Nano zero-valent iron (nZVI) has a great potential for arsenic removal, but it would form aggregates easily and consume largely by H+ in the strongly acidic solution. In this work, 15%CaO doped with nZVI (15%CaO-nZVI) was successfully synthesized from a simplified ball milling mixture combined with a hydrogen reduction method, which had a high adsorption capacity for As(V) removal from high-arsenic acid wastewater. More than 97% As(V) was removed by 15%CaO-nZVI under the optimum reaction conditions of pH 1.34, initial As(V) concentration 16.21 g/L, and molar ratio of Fe/As (nFe/nAs) 2.5:1. The effluent pH solution was weakly acidic 6.72, and the secondary arsenic removal treatment reduced the solid waste and improved arsenic grade in slag from the mass fraction of 20.02% to 29.07%. Multiple mechanisms including Ca2+ enhanced effect, adsorption, reduction, and co-precipitation coexisted for As(V) removal from high-arsenic acid wastewater. Doping of CaO might lead to improving cracking channels which was benefit for electronic transmission and the confusion of atomic distribution. The in situ weak alkaline environment generated on the surface of 15%CaO-nZVI would increase the content of γ-Fe2O3/Fe3O4, which was in favor for As(V) adsorption. In addition, H+ in the strongly acidic solution could accelerate corrosion of 15%CaO-nZVI and abundant fresh and reactive iron oxides continuously generated, which would provide plenty specific reactive site and fast charge transfer and ionic mobility for arsenic removal.

Two new alkaloids from Dendrobium nobile Lindl. exhibited neuroprotective activity, and dendrobine alleviated Aß1-42 -induced apoptosis by inhibiting CDK5 activation in PC12 cells.

Dendrobium nobile Lindl. is registered in the Chinese Pharmacopoeia as a traditional medicine. Phytochemical investigation of the ethanol extract of D. nobile Lindl. stems yielded three alkaloid compounds, including two new compounds dendroxine B (2) and denrine B (3) as well as one known compound dendrobine (1). Here, we identified the structure of these compounds using spectroscopic analyses and compared them with those described in previous studies. Compounds 1-3 were found to show protective effect against amyloid-ß 1-42 (Aß1-42 )-induced neurotoxicity in rat pheochromocytoma (PC12) cells, among which dendrobine exhibited the most significant neuroprotective effect. Hoechst 33342/propidium iodide staining indicated that dendrobine ameliorated Aß1-42 -induced apoptosis. Moreover, quantitative real-time polymerase chain reaction and western blot analysis analysis demonstrated that dendrobine suppressed the activation of cyclin-dependent kinase 5 (CDK5), upregulated Bcl-2 expression, and downregulated Bax, cyto-c, and caspase-3 expression. Molecular docking analysis and surface plasmon resonance assay suggested that dendrobine directly bound to CDK5 protein with a KD value of 2.05 × 10-4 M. In summary, alkaloids are the neuroprotective constituents of D. nobile Lindl., and dendrobine protected PC12 cells against Aß1-42 -induced apoptosis by inhibiting CDK5 activation.

Enhanced removal of aqueous Cr(VI) by the in situ iron loaded activated carbon through a facile impregnation with Fe(II) and Fe(VI) two step method: Mechanism study.

In this study, a novel in situ iron-loaded activated carbon (AFPAC) was prepared by a FeSO4/K2FeO4 impregnation and oxidation combination two-step supported on activated carbon for enhanced removal of Cr(VI) from aqueous solutions. Cr(VI) removal efficiency greatly increased by AFPAC more than 70% than that of fresh activated carbon (AC), which is due to rich iron oxides formed in situ and the synergistic effect between iron oxides and activated carbon. Cr(VI) adsorption behaviors on AFPAC under different water quality parameters were investigated. The maximum monolayer adsorption capacities for Cr(VI) by AFPAC are as high as 26.24 mg/g, 28.65 mg/g, and 32.05 mg/g at 25 °C, 35 °C and 45 °C at pH 4, respectively. Density functional theory (DFT) results showed that the adsorption energy of K2Cr2O7 on the surface of FeOOH was - 2.52 eV, which was greater than that on the surface of bare AC, and more charge transfer occurred during the adsorption of K2Cr2O7 on the surface of FeOOH, greatly promoting the formation of Cr = O-Fe. Cr(VI) removal by AFPAC included electrostatic attraction, redox reaction, coordinate complexation, and co-precipitation. Cr(VI) adsorption process on AFPAC consisted of the three reaction steps: (1) AFPAC was fast protonation and Cr2O72- would electrostatically attract to the positively charged AFPAC surface. (2) Cr2O72- was reduced into Cr2O3 by the carbons bond to the oxygen functionalities on activated carbon and the redox reaction process of FeSO4 and K2FeO4. (3) The inner-sphere complexes were formed, and adsorbed on AFPAC by iron oxides and then co-precipitation.

Characteristics and mechanisms of As(III) removal by potassium ferrate coupled with Al-based coagulants: Analysis of aluminum speciation distribution and transformation.

This study was carried out to investigate the enhanced removal of arsenite (As(III)) by potassium ferrate (K2FeO4) coupled with three Al-based coagulants, which focused innovatively on the distribution and transformation of hydrolyzed aluminum species as well as the mechanism of K2FeO4 interacted with different aluminum hydrolyzed polymers during As(III) removal. Results demonstrated that As(III) removal efficiency could be substantially elevated by K2FeO4 coupled with three Al-based coagulants treatment and the optimum As(III) removal effect was occurred at pH 6 with more than 97%. K2FeO4 showed a great effect on the distribution and transformation of aluminum hydrolyzed polymers and then coupled with a variety of aluminum species produced by the hydrolysis of aluminum coagulants for arsenic removal. During enhanced coagulation, arsenic removal by AlCl3 was main through the charge neutralization of in situ Al13 and the sweep flocculation of Al(OH)3, while PACl1 mainly depended on the charge neutralization of preformed Al13 and the bridging adsorption of Al13 aggregates, whereas PACl2 mainly relied on the sweep flocculation of Al(OH)3. This study provided a new insight into the distribution and transformation of aluminum species for the mechanism of As(III) removal by K2FeO4 coupled with different Al-based coagulants.

Highly efficient removal of arsenate and arsenite with potassium ferrate: role of in situ formed ferric nanoparticle.

It is well known the capacity of potassium ferrate (Fe(VI)) for the oxidation of pollutants or co-precipitation and adsorption of hazardous species. However, little information has been paid on the adsorption and co-precipitation contribution of the Fe(VI) resultant nanoparticles, the in situ hydrolytic ferric iron oxides. Here, the removal of arsenate (As(V)) and arsenite (As(III)) by Fe(VI) was investigated, which focused on the interaction mechanisms of Fe(VI) with arsenic, especially in the contribution of the co-precipitation and adsorption of its hydrolytic ferric iron oxides. pH and Fe(VI) played significant roles on arsenic removal; over 97.8% and 98.1% of As(V) and As(III) removal were observed when Fe(VI):As(V) and Fe(VI):As(III) were 24:1 and 16:1 at pH 4, respectively. The removal of As(V) and As(III) by in situ and ex situ formed hydrolytic ferric iron oxides was examined respectively. The results revealed that As(III) was oxidized by Fe(VI) to As(V), and then was removed though co-precipitation and adsorption by the hydrolytic ferric iron oxides with the contribution content was about 1:3. For As(V), it could be removed directly by the in situ formed particles from Fe(VI) through co-precipitation and adsorption with the contribution content was about 1:1.5. By comparison, As(III) and As(V) were mainly removed through adsorption by the 30-min hydrolytic ferric iron oxides during the ex situ process. The hydrolytic ferric iron oxides size was obviously different in the process of in situ and ex situ, possessing abundant and multiple morphological structures ferric oxides, which was conducive for the efficient removal of arsenic. This study would provide a new perspective for understanding the potential of Fe(VI) treatment on arsenic control.

Efficient removal of cadmium by salts modified-biochar: Performance assessment, theoretical calculation, and quantitative mechanism analysis.

Modified biochar is a feasible adsorbent to solve cadmium pollution in water. However, few studies could elucidate the mechanism of cadmium adsorption by biochar from a molecular perspective. Furthermore, traditional modification methods are costly and have the risk of secondary contamination. Hence, several environmentally friendly sodium salts were used to modify the water chestnut shell-based biochar and employ it in the Cd2+ adsorption in this work. The modification of sodium salt could effectively improve the specific surface area and aromaticity of biochar. Na3PO4 modified biochar exhibited the highest Cd2+ adsorption capacity (112.78 mg/g). The adsorption of Cd2+ onto biochar was an endothermic, monolayer, chemisorption process accompanied by intraparticle diffusion. Microscopically, the enhancement of aromatization after modification made Cd2+ more likely to interact with the regions rich in π electrons and lone pair electrons. This study provided a new research perspective and application guidance for heavy metal adsorption on biochar.

Bio-flocculation of Microcystis aeruginosa by using fungal pellets of Aspergillus oryzae: Performance and mechanism.

Algal blooms caused by eutrophication are global phenomena that seriously threaten the sustainable use of freshwater resources. Traditional water treatment chemicals often typically lead to high levels of residue and cause damage to the morphology of algal cells. This study investigated an eco-friendly fungal bio-flocculant, Aspergillus oryzae, to remove the representative microalgae (Microcystis aeruginosa). Furthermore, it explored crucial flocculation parameters, adsorption kinetics, and thermodynamics of microalgae using A. oryzae. Accordingly, a flocculation efficiency of >95% was achieved when the fungus was cultured for six days, flocculant dosage was 11 g/L, rotation speed was 100 rpm, temperature was 25 °C, flocculation time was 5 h, and pH ranged between 4.0 and 9.0. KEGG analysis based on the genomic data, and chemical composition analysis revealed that proteins and polysaccharides were the major components of metabolites. Zeta potential analysis, scanning electron microscopy, three-dimensional fluorescence, X-ray spectroscopy, and infrared spectroscopy, electrostatic attraction revealed that electrostatic attraction promoted the destabilization and aggregation of microalgae. Additionally, hyphal surface adsorption and chemisorption from extracellular proteins and exopolysaccharides aided in the removal of microalgae. Therefore, fungi-based bio-flocculants have the potential to remove microalgae in a simple, effective, and eco-friendly manner without the complex extraction of extracellular metabolites.

The effect of bacterial functional characteristics on the spread of antibiotic resistance genes in Expanded Granular Sludge Bed reactor treating the antibiotic wastewater.

To explore the fate and spreading mechanism of antibiotics resistance genes (ARGs) in antibiotics wastewater system, a laboratory-scale (1.47 L) Expanded Granular Sludge Bed (EGSB) bioreactor was implemented. The operating parameters temperature (T) and hydraulic retention time (HRT) were mainly considered. This result showed the removal of ARGs and COD was asynchronous, and the recovery speed of ARGs removal was slower than that COD removal. The decreasing T was attributed to the high growth rate of ARGs host bacteria, while the shortened HRT could promote the horizontal and vertical gene transfer of ARGs in the sludge. The analysis result of potential bacterial host showed more than half of the potential host bacteria carried 2 or more ARGs and suggested an indirect mechanism of co-selection of multiple ARGs. Phylogenetic Investigation of Communities by Reconstruction of Unobserved States (PICRUSt) was used to investigate the functional characteristics of bacterial community. This result showed the bacterial functional genes contributed 40.41% to the abundance change of ARGs in the sludge, which was higher that of bacterial community. And the function genes of "aromatic hydrocarbon degradation", "Replication, recombination and repair proteins" and "Flagellar assembly" were mainly correlated with the transfer of ARGs in the sludge. This study further revealed the mechanism of ARGs spread in the EGSB system, which would provide new ideas for the development of ARGs reduction technology.

Novel sodium bicarbonate activation of cassava ethanol sludge derived biochar for removing tetracycline from aqueous solution: Performance assessment and mechanism insight.

NaHCO3 was used as a novel activator to produce cassava ethanol sludge-based biochar. The NaHCO3-activated biochar showed superior adsorption capacity for tetracycline (154.45 mg/g) than raw biochar (34.04 mg/g). Orthogonal experiments confirmed the optimal preparation conditions of biochar. Increasing adsorbent dosage and temperature facilitated tetracycline removal. The maximum removal was 92.60% at pH = 3.0. Calcium ions and alkalinity decreased tetracycline removal. The time for attaining equilibrium was extended with increasing tetracycline concentration, but the equilibrium could be completed within 24 h. Langmuir model fitted the equilibrium data well. Kinetics process followed the Elovich model. The adsorption rate was controlled by both intraparticle and liquid film diffusion and the process was endothermic and spontaneous. The electrostatic attraction, hydrogen bonding, π-π interactions, and pore-filling were involved in the adsorption mechanism. The findings may provide an underlying guide for sludge disposal and removal of tetracycline from wastewater in practical application.

Flocculation of emulsified oily wastewater by using functional grafting modified chitosan: The effect of cationic and hydrophobic structure.

In this work, modified chitosan flocculants (MCS) was synthesized by using chitosan (CS), acrylamide, cationic monomers and hydrophobic monomers via low-pressure UV-initiated copolymerization. The flocculation performance of MCS was evaluated in emulsified oily wastewater treatment. The effect of cationic and hydrophobic structure on oil removal was studied, and the interactions between these functional groups and the components in oil were also analyzed. Results suggested that MCS flocculants exhibited excellent oil removal efficiency in a wide pH range (2.0‒10). The flocculation efficiency of 91 % was achieved at the dosages of 0.6 mL/L (6 mg/L). During pH of 2.0-10, the optimal cationic and hydrophobic monomer was DMC and VT, respectively. Silane groups were favorable for oil removal than the other hydrophobic structures. The cationic groups expanded the optimal pH range of MCS in flocculation, whereas hydrophobic groups considerably reduced the dosage of MCS. The experimental results showed that alkane, cyclic aromatic hydrocarbon compounds in oil can be easily removed by using MC4, whereas cycloalkanes compounds was effectively removed by MC6 and MC7 because of preferable demulsification capacity, and the hydrophobic interaction, interfacial adsorption and electrostatic attraction played the dominant in flocculation. Thus, the synthesized MCS is favorable for emulsified oily wastewater treatment.

Adsorptive removal of gallic acid from aqueous solution onto magnetic ion exchange resin.

Finding an appropriate adsorbent with high adsorption capacity, quick adsorption kinetics and easy regeneration was crucial to the removal of gallic acid (GA) from water and wastewater. Our aims were to investigate whether a magnetic ion exchange (MIEX) resin had the three merits mentioned above, and investigate the feasibility of GA adsorption on MIEX resin, and the adsorption kinetics, equilibrium, thermodynamics, regeneration and mechanism using batch tests. The uptake of GA increased with increasing GA concentration. The GA concentration influenced the time needed to reach equilibrium, but the adsorption could be completed within 120 min. Elevating temperature facilitated the GA removal. The removal percent remained above 95.0% at pH 5.0-11.0. Carbonate and bicarbonate promoted the GA removal; conversely chloride, sulfate and nitrate restrained the GA removal significantly. The adsorption kinetics could be fitted well with the pseudo second-order model, and the film diffusion governed the whole adsorption rate. The equilibrium data followed the Redlich-Peterson isotherm model. The adsorption was a spontaneous, endothermic and entropy driven process. The ion exchange dominated the removal mechanism. The spent MIEX resin was well regenerated by sodium chloride. Therefore, MIEX resin is a potential adsorbent for removing GA quickly and efficiently from water and wastewater.

Profiles and risk assessment of phthalate acid esters (PAEs) in drinking water sources and treatment plants, East China.

This study is the first report describing the occurrence of 15 phthalate acid esters (PAEs) in the three typical water sources of YiXing City, Taihu Upper-River Basin, East China. The fate of target PAEs in the Jiubin drinking water treatment plant (JTP) was also analyzed. The amounts of Σ15PAE in the Hengshan (HS), Youche (YC), and Xijiu (XJ) water sources were relatively moderate, with mean values of 360, 357, and 697 ng L-1, respectively. Bis(2-ethylhexyl) phthalate (DEHP) dominated the PAE concentration, making up 80% of the 15 total PAEs. The highest levels of Σ15PAE were found in HS, YC, and XJ in March 2015, January 2015, and July 2014, respectively. The occurrence and concentrations of these compounds were spatially dependent, and the mean concentrations of Σ15PAE in HS, YC, and XJ samples increased from the surface layer to the bottom layer with varied percentage increases. The removal efficiency of the PAEs in the finished water varied markedly, and the removal of PAEs by the JTP ranged from 12.8 to 64.5%. The potential ecosystem risk assessment indicated that the risk of PAEs was relatively low in these three water sources. However, risks posed by PAEs due to drinking water still exist; therefore, special attention should be paid to source control in the JTP, and advanced treatment processes for drinking water supplies should be implemented.

Influence of humic acid on the removal of arsenate and arsenic by ferric chloride: effects of pH, As/Fe ratio, initial As concentration, and co-existing solutes.

The influence of humic acid (HA) on the removal of arsenic by FeCl3 was systematically studied in this paper. Jar tests were performed to investigate the influence on arsenic during FeCl3 coagulation of the pH adjusting method, the initial As/Fe ratio, the equilibrium As concentration, and co-occurring anions and cations. Compared with results in HA-free systems, the removal trends of arsenic in HA solutions were quite different. It was found that As(V) removal was higher at low equilibrium concentration, yet the opposite was true for As(III) removal. The presence of HA influenced the effective number of active sites for arsenic removal by FeCl3 flocculation. In addition, in the presence of HA, the impacts of co-existing solutions on arsenic removal were also different from that of an HA-free system. This study examined the influence of co-occurring anions, such as phosphate, sulfate, and silicate on arsenic removal, depending on their ability to compete for sorption sites and to hinder or facilitate the aggregation of ferric hydroxide flocs. The presence of Ca2+ or Cd2+ significantly increased arsenic removal at higher pH. Low concentrations of dissolved HA and high concentrations of colloid affected the adsorption of arsenic onto iron oxide. The influence of HA on the adsorption of arsenic onto iron oxide primarily depended on the relative content of the dissolved and mineral combination states of HA and the interface combination forms.

Synthesized heterogeneous Fenton-like goethite (FeOOH) catalyst for degradation of p-chloronitrobenzene.

The removal of p-chloronitrobenzene (pCNB) was investigated by a heterogeneous Fenton-like system using a laboratory synthesized goethite (FeOOH) as catalyst. The influencing factors and the degradation pathway of pCNB were also evaluated. With a stronger catalytic activity than Fe(2+) catalyst, the synthesized FeOOH catalyst can significantly promote the decomposition of H(2)O(2), and the decomposition product hydroxyl radicals (·OH) can oxidize pCNB in the water effectively. The FeOOH catalyst can also adsorb a certain amount of pCNB, and the adsorption effect is related to the amount of FeOOH and the initial pH value of solution. The results of liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS) showed that the main intermediate products were phenolic compounds and carbonyl compounds. About 60% of pCNB was mineralized during the catalytic oxidation, and chlorine and nitro groups on benzene ring were converted into Cl(-) and NO(3)(-) after being attacked.