Wrinkle- and Edge-Adsorption of Aromatic Compounds on Graphene Oxide as Revealed by Atomic Force Microscopy, Molecular Dynamics Simulation, and Density Functional Theory.

In this work, the favorable adsorption sites of aromatic compounds (ACs) on graphene oxide (GO) are characterized with both experimental and theoretical approaches. The results show that ACs exhibit a strong preference in adsorbing near the wrinkles and edges. Further analyses reveal that the edge-adsorption is mainly guided by the stronger π-π interaction near edges, accompanied by a stronger hydrogen bond interaction between carboxyl groups and ACs. Additionally, the water-mediated steric hindrance and flexibility of carboxyl groups also contribute to the edge-adsorption. A higher density of atoms and electrons is the main mechanism for the wrinkle-adsorption, and structural investigations indicate that the roughness serving as a steric hindrance for the ACs migration also contributes to the wrinkle-adsorption. This wrinkle- and edge-adsorption pattern will shed light on the design of GO-related environmental materials.

New Insight into the Aggregation of Graphene Oxide Using Molecular Dynamics Simulations and Extended Derjaguin-Landau-Verwey-Overbeek Theory.

A comparative experimental and molecular dynamics (MD) simulation study was carried out to investigate the aggregation of graphene oxide (GO). Mechanisms behind the effects of solution chemistries (pH, metal ions, and tannic acid (TA)) and GO topology (carboxyl content, GO size, and GO thickness) were uncovered. For example, MD results showed that more hydrogen bonds formed between GO and water at higher pH, according well with the increased hydrophilicity of GO calculated based on contact angle measurements. Radial distribution functions analysis suggested Ca2+ interacted more strongly with GO than Na+, which explained the experimental observations that Ca2+ was more effective in accelerating the aggregation process than Na+. The adsorption-bridging and steric effects of TA were simulated, and TA was found to be unfolded upon wrapping on GOs, leading to an increased capacity for ion and solvent binding. The evaluations of contributions to GO hydrophilicity, electrostatic energy, and intensities of interactions with metal ions indicated the carboxyl group is the essential functional group in mediating the stability of GO. Overall, by combining MD simulations with experimental measurements, we provided molecular-level understandings toward the aggregation of GO, indicating MD, if used properly, can be applied as a useful tool to obtain insights into the aggregation of nanomaterials.

Effects of different modifying agents on the preparation and properties of coagulants derived from excess sludge.

The contents and kinds of oxygen-containing functional groups are very significant when preparing cationic hydrochar coagulants via graft copolymerization. Herein, the hydrothermal conditions to produce sludge-based hydrochar (SBC) precursors were optimized by introducing different kinds and amounts of modifying agents (i.e., HCOOH, citric acid (CA), H2SO4, and H2O2), then the surface properties and flocculation performance of derived cationic coagulants (SBC-g-DMC) were studied. Results showed that the utilization of four modifiers raised the acidic groups on the SBC surface; thereinto, the presence of CA could evidently increase the content of phenolic hydroxyl groups. After DMC monomer grafting, the formed coagulants possess positive zeta potentials over a wide pH range (i.e., 3.0 ~ 11.0), showing a typical cationic property. The grafting ratio and efficiency, as well as the cationic degree of coagulants prepared with different SBC precursors follow a descending order of SBCCA-g-DMC > [Formula: see text]-g-DMC > SBCHCOOH-g-DMC > [Formula: see text]-g-DMC; thus, SBCCA-g-DMC coagulant with the best grafting result shows a superior flocculation performance. When a dosage of 4 mg/L was adopted, the average turbidity removal rate of SBCCA-g-DMC could reach up to 94.44%. Meanwhile, due to the possible and robust oxidation with the initiator, H2O2 seems not a perfect modifier for SBC preparation. This study could provide an essential reference for the optimal synthesis of SBC and its based coagulants for organic matter recovery and pollutant removal.

Long-term effects of Ag NPs on denitrification in sediment: Importance of Ag NPs exposure ways in aquatic ecosystems.

The widespread use of silver nanoparticles (Ag NPs) inevitably leads to their increasing release into aquatic systems, with studies indicating that the mode of Ag NPs entry into water significantly affects their toxicity and ecological risks. However, there is a lack of research on the impact of different exposure ways of Ag NPs on functional bacteria in sediment. This study investigates the long-term influence of Ag NPs on denitrification process in sediments by comparing denitrifies responses to single (pulse injection of 10 mg/L) and repetitive (1 mg/L × 10 times) Ag NPs treatments over 60-day incubation. Results showed that a single exposure of 10 mg/L Ag NPs caused an obvious toxicity on activity and abundance of denitrifying bacteria on the first 30 days, reflecting by the decreased NADH amount, ETS activity, NIR and NOS activity, and nirK gene copy number, which resulted in a significant decline of denitrification rate in sediments (from 0.59 to 0.64 to 0.41-0.47 µmol15N L-1 h-1). While inhibition was mitigated with time and denitrification process recovered to the normal at the end of the experiment, the accumulated nitrate generated in the system showed that the recovery of microbial function did not mean the restoration of aquatic ecosystem after pollution. Differently, the repetitive exposure of 1 mg/L Ag NPs exhibited the evident inhibition on metabolism, abundance, and function of denitrifiers on Day 60, due to the accumulated amount of Ag NPs with the increased dosing number, indicating that the accumulated toxicity on functional microorganic community of repetitive exposure in less toxic concentration. Our study highlights the importance of Ag NPs entry pathways into aquatic ecosystem on their ecological risks, which affected dynamic responses of microbial function to Ag NPs.

Preparation of cationic aggregates derived from sewage sludge for efficient capture of organic matter.

Capturing the abundant organic matter residing in wastewater can not only reduce the emission of CO2 from the source, but the enriched organics can also be used for anaerobic fermentation to generate and offset energy consumption in wastewater treatment processes. The key is to find or develop low-cost materials that can capture organic matter. Herein, sewage sludge-derived cationic aggregates (SBC-g-DMC) were successfully prepared via a hydrothermal carbonization process coupled with a graft copolymerization reaction for recovering organic matter from wastewater. Based upon preliminary screening of synthesized SBC-g-DMC aggregates regarding grafting rate, cationic degree, and flocculation performance, SBC-g-DMC2.5 aggregate prepared with 60 mg of initiator, DMC-to-SBC mass ratio of 2.5:1, 70 °C, and 2 h of reaction time was selected for further characterization and evaluation. Results showed that SBC-g-DMC2.5 aggregate has a positively-charged surface over a wide pH range of 3-11 and a hierarchical micro-/nano-structure, endowing it with an excellent organic matter capture efficiency (97.2% of pCOD, 68.8% of cCOD, and 71.2% of tCOD). Meanwhile, SBC-g-DMC2.5 exhibits inappreciable trapping ability for the dissolved COD, NH3-N, and PO43-, guaranteeing the regular running of subsequent biological treatment units. Electronic neutralization, adsorption bridging, and sweep coagulation between cationic aggregates surface and organic matter were identified as the primary mechanisms for SBC-g-DMC2.5 to capture organics. This development is expected to provide a theoretical reference for sewage sludge disposal, carbon reduction, and energy recovery during municipal wastewater treatment.

Effect of microplastics on the adherence of coexisting background organic contaminants to natural organic matter in water.

Microplastics (MPs) may interact with background organic substances (including natural organic matter and organic pollutants) after entering the aquatic environment and affect their original binding. Thus, the interaction of MPs with background organic substances (i.e., humic acid (HA), polychlorinated biphenyls (PCBs), and hydroxy PCBs) were elucidated. According to the results, PCB and hydroxy PCB displayed a strong propensity to adhere to HAs in the absence of MPs. However, the PCBs and hydroxy PCBs that were initially bound to HAs shifted from HAs to MPs in the presence of MPs. Further analysis demonstrated that this transfer was dominated by van der Waals interactions, with hydrogen bond interactions as an additional driving force. Upon the interaction, large MPs-HA-PCB/ hydroxy PCB aggregates with MPs as the core and HAs as the outermost layer were formed. Significant changes in the properties of background organic matter, including the distribution of PCB/hydroxy PCB around HA, diffusion coefficient, and hydrogen bond networks in the HA-PCB/ hydroxy PCB domains, occurred during the MP-HA-PCB/hydroxy PCB interaction. These results provide molecular-level evidence that the intrusion of MPs changes the binding preference of background organic pollutants and can lead to a redistribution of background organic pollutants.

Development and application of lanthanum peroxide loaded sepiolite nanocomposites for simultaneous removal of phosphate and inhibition of cyanobacteria growth.

The ecological and environmental problem caused by harmful algal blooms (HABs) is challenging to humans. The simultaneous elimination of cyanobacteria and phosphate from eutrophic waters is of great importance. Herein, a new lanthanum peroxide-loaded sepiolite nanocomposite was fabricated via a facile in-situ co-precipitation method and demonstrated the excellent properties on removal of phosphate and inhibition of cyanobacteria growth. The optimized nanocomposite (termed as LPS30) prepared with a La-to-Sepiolite mass ratio of 0.3:1 demonstrated the best cyanobacteria removal with an effective duration of at least 3 months, due to the even dispersion of high-content LP nanoparticles in the sepiolite. LPS30 exhibited a high phosphate uptake (52.68 mg-P/g), fast uptake kinetics (∼45 min to reach 80% of ultimate uptake), and relatively higher selectivity in the presence of competing matters. The pH-dependent phosphate sorption resulted from the ligand exchange between phosphate and surface functional groups (e.g., peroxo and hydroxyls), and the electrostatic attraction. The efficient and long-lasting inhibition for cyanobacteria regrowth was attributed to the combined effect of the oxidative species (i.e., LaOO-) and the efficient removal of phosphate through the coagulation flocs. Our study demonstrated that LPS30 is a promising material to simultaneously treat phosphate and algae for HABs management.

Remarkable phosphate removal and recovery from wastewater by magnetically recyclable La2O2CO3/γ-Fe2O3 nanocomposites.

Owing to the twin problems of eutrophication and global phosphorus (P) scarcity, the removal and recovery of phosphate from water and wastewater have received increasing attention. Herein, magnetically recyclable La2O2CO3/γ-Fe2O3 adsorbents were rationally designed by derivation from La/Fe binary metal organic framework (MOF) precursors via calcination treatment. Based upon preliminary screening of as-prepared La2O2CO3/γ-Fe2O3 nanocomposites with different La-to-Fe molar ratios in terms of phosphate sorption capacity and magnetic property as well as La content, La2O2CO3/γ-Fe2O3 nanocomposite with a La-to-Fe molar ratio of 2:1 was selected for further characterization and adsorption performance evaluation. Batch adsorption experiments showed that La2O2CO3/γ-Fe2O3 (2:1) adsorbent exhibited a remarkable phosphate sorption capacity of 134.82 mg P/g, a fast sorption kinetic, strong selectivity for phosphate in the presence of co-existing anions, and a wide applicable pH range of 3-9. Furthermore, La2O2CO3/γ-Fe2O3 (2:1) sorbent displayed an excellent sorption performance for low-concentration wastewater, a low dosage of 0.1 g/L was sufficiently enough for reducing P-concentration from 0.5 mg P/L to below 10 µg P/L within 20 min. In a real sewage of 2.68 mg P/L, 0.2 g/L of sorbent could reduce the concentration of phosphate to <0.01 mg P/L within 50 min. Moreover, over 83.1 % of original sorption capacity could be retained after 5 consecutive regeneration cycles, showing great regenerative performance of the adsorbent. These development is expected to be meaningful for practical water purification.

Linear solvation energy relationship to predict the adsorption of aromatic contaminants on graphene oxide.

In this study, adsorption capability of aromatic contaminants on graphene oxide (GO) was predicted using linear solvation energy relationship (LSER) model for the first time. Adsorption data of 44 aromatic compounds collected from literature and our experimental results were used to establish LSER models with multiple linear regression. High value of R2 (0.919), strong robustness (QLoo2 = 0.862), and desirable predictability (Qext2 = 0.834) demonstrated the model worked well for predicting the adsorption of small aromatic contaminants (descriptor V＜3.099) on GO. The adsorption process was governed by the ability of cavity formation and dispersion forces captured by vV and hydrogen-bond interactions captured by bB. Effect of equilibrium concentrations and properties of GO on the model were explored; and the results indicated that upon an increase of equilibrium concentration, the values of regression coefficients (a, b, v, e, and s) changed at different levels. The oxygen content normalization of logK0.001 decreased the value of b dramatically; however, no obvious changes of the model deduced by the surface area normalization of logK0.001 were witnessed. Overall, our study showed that LSER model provided a potential approach for exploring the adsorption of organic compounds on GO.