Facile Preparation of Magnetic CuFe2O4 on Sepiolite/GO Nanocomposites for Efficient Removal of Pb(II) and Cd(II) from Aqueous Solution.

CuFe2O4 nanoparticles were synthesized and immobilized on sepiolite fibers and graphene oxide sheets, producing a CuFe2O4/sepiolite/GO (CFSG) nanocomposite via a facile single-pot method. The synthesized nanocomposite was characterized using TEM, FTIR, SEM-EDX, XRD, and TGA techniques to determine its composition, structure, and thermal stability. The adsorptive removal of Pb(II) and Cd(II) heavy metal ions from aqueous solutions was studied using the synthesized CFSG nanocomposite. Adsorption parameters such as CFSG loading, pH, contact time, and temperature were investigated. The CFGS nanocomposite showed a higher Pb(II) removal (qm = 238.1 mg/g) compared to Cd(II) (qm = 14.97 mg/g) in a Pb(II) and Cd(II) binary system. The Pb(II) and Cd(II) adsorption fitted well with the Langmuir model, followed by the pseudo-second-order model, and was found spontaneous. Adsorption thermodynamic analysis showed that the Pb(II) adsorption process was exothermic while Cd(II) adsorption was endothermic. The CuFe2O4 nanoparticles on the CFSG surface could facilitate the adsorption of heavy metal ions through electrostatic interaction and complexation processes.

Carbon dioxide adsorbents from flame-made diesel soot nanoparticles.

Carbon dioxide (CO2) is the top contributor to global warming. On the other, soot particles formed during fuel combustion and released into the atmosphere are harmful and also contribute to global warming. It would therefore be highly advantageous to capture soot and make use of it as a feedstock to synthesize carbon-based materials for applications such as carbon dioxide adsorption. In this work, flame-made diesel soot nanoparticles were used to produce a variety of activated carbons by combined oxidative treatment with hydrogen peroxide (H2O2) and potassium hydroxide (KOH), and their performance towards CO2 adsorption was evaluated. The effect of the chemical activation of soot with H2O2 for different reaction times and with KOH on the physicochemical properties of the activated carbons was investigated and compared to fresh soot. Interestingly, hollow aggregates of carbonaceous nanoparticles of a high interplanar distance, reduced polycyclic aromatic hydrocarbons (PAH) size, shorter PAH stacks, mesoporous structure, and a high content of oxygen functionalities along with other structural defects in PAHs were obtained in the synthesized activated carbons. Among the various analysis techniques employed, Raman spectroscopy indicated that the ID/IG ratio in soot decreased after simultaneous chemical treatment, though it did not indicate any enhancement in the graphitic character since the carbonyl and carboxylic containing PAHs and monovacancies (which cause defects in PAHs) also contribute to the increase in the intensity of the graphitic band. The activated carbons possessed promising CO2 adsorption capacities, adsorption kinetics and CO2/N2 selectivity. For example, one of the activated carbons, following H2O2 treatment for 9 h and a subsequent KOH activation, exhibited a CO2 adsorption capacity of 1.78 mmol/g at 1 bar and 25 °C, representing an increase of 161 % in capacity as compared to fresh soot. Hollow aggregates of carbonaceous nanoparticles consisting of shorter PAHs with a larger number of defects led to enhanced CO2 adsorption rate and CO2/N2 selectivity on activated carbons.

Graphene Oxide-alginate Hydrogel for Drawing Water through an Osmotic Membrane.

We report the preparation and evaluation of graphene oxide (GO)-enhanced alginate hydrogels for drawing water across an osmotic desalination membrane. GO-incorporated calcium alginate hydrogels (GO-HG) and pure calcium alginate hydrogels (P-HG) were synthesized for this study. Environmental scanning electron microscopy, water contact angle, and water uptake tests showed both samples to be strongly hydrophilic. The synthesized hydrogels demonstrated the ability to successfully and continuously draw water through a selective osmotic membrane in experiments. This was driven by the surface energy gradient-induced negative pressure between the more hydrophilic hydrogel and less hydrophilic membrane surface. The GO-HG was found to draw 21.2% more water than the P-HG, owing to the flexible GO nanosheets, which can be easily incorporated into the hydrogel framework. The GO nanosheets not only offer more hydrophilic functional sites but also enhance the connectivity within the alginate hydrogel framework so as to enhance the water production performance. The average amount of water drawn through the membrane by the GO-HG and the P-HG is 23.4 ± 0.9 g and 19.3 ± 1.8 g, respectively. It was found that no external stimuli were needed as water flows through the hydrogel due to gravitational force. The GO-enhanced alginate hydrogel, combined with the osmotic membrane, is a promising surface energy gradient-driven functional material for water purification and desalination without applying external pressure.

Highly Permeable MoS2 Nanosheet Porous Membrane for Organic Matter Removal.

MoS2 nanosheets were synthesized by a bottom-up green chemical process where l-cysteine was used as a sulfur precursor. With specific concentrations, molar ratio of reactants, and pre-mixing conditions, MoS2 nanosheets of 200-300 nm in size and 4.2 nm in average thickness were successfully obtained. Porous membranes were then prepared by depositing the MoS2 nanosheet suspension on a 0.1 µm pore size poly(vinylidene difluoride) membrane filter in a multiple batch procedure. The membrane deposited with 12 batches of MoS2 nanosheets achieved 93.78% removal of bovine serum albumin. Acid red removal of 95.65% was also achieved after the second filtration pass. The porous MoS2 nanosheet membrane also demonstrated a high water flux of 182 ± 2.0 L/(m2 h). This result overcame the trade-off between selectivity and permeability faced by polymeric ultrafiltration membranes. The MoS2 nanosheets as building blocks formed not only intersheet slit pores with a narrow half-width to restrict the passage of organic molecules but also macro-channels allowing easy passage of water. The assembled MoS2 nanosheet membrane delivered promising separation of protein molecules and a high flux, attributing to its porous nanostructure, and could be a potential membrane for various water applications.

2D MoS2 nanoplatelets for fouling resistant membrane surface.

2D Molybdenum disulfide (MoS2) nanoplatelets were synthesized via a green bottom-up strategy using non-toxic l-Cysteine as sulfur source. Thehydrophobic MoS2 nanoplatelets assisted by hydrophilic 3-(3, 4-dihydroxyphenyl)-l-alanine (l-DOPA) were coated on a thin film composite nanofiltration (TFC-NFG) membrane. The accelerated fouling experiments were conducted by usingbovine serum albumin (BSA) asmodel organic foulant,and MoS2 coated membrane demonstrated excellent resistance with almost no flux decline within first hour of filtration, whereas the uncoated membrane showed flux decline immediately from the beginning of the experiment. After 5-hour filtration, the flux reduced by only 26% for MoS2 coated membrane with a higher flux recovery rate of 85.4% after washing by de-ionized (DI) water, whereas 45% flux decline was observed for uncoated membrane with lower flux recovery of 68%.These antifouling effects attributed by MoS2coated membrane were underpinned by combined unique interfacial properties offered by 2D tri-atomic layered MoS2morphology including dispersive surface tension, reduced surface roughness, weaker MoS2-foulant interactive forces, and negatively charged surface. This research positively confirms the role of 2D MoS2 nanoplatelets as an anti-fouling coating on membranes and brings up more possibility for applying other nanomaterials in 2D family in water applications such as desalination and water treatment.

Electrostatically coupled SiO2 nanoparticles/poly (L-DOPA) antifouling coating on a nanofiltration membrane.

In this work, the fouling resistance of TFC (thin film composite) nanofiltration membranes have been enhanced using an electrostatically coupled SiO2 (silica dioxide) nanoparticles/poly(L-DOPA) (3-(3,4-dihydroxyphenyl)-l-alanine) antifouling coating. SiO2 nanoparticles were synthesized in different size ranges and combined with L-DOPA; and then coated as an anti-fouling layer on the membrane surface by recirculated deposition. Membranes were coated with S-NP (silica nanoparticles) in small (19.8 nm), medium (31.6 nm) and large (110.1 nm) sizes. The zwitterionic compound L-DOPA in the form of self-polymerized poly(L-DOPA) (PDOPA) helped with the attachment of the S-NP to the membrane surface. It was confirmed by AFM (atomic force microscopy) measurement that coating of membranes led to an increase in hydrophilicity and reduction in surface roughness, which in turn led to a 60% reduction in the adhesion force of the foulant on the membrane as compared to the neat membrane. The modified membranes experienced almost no flux decline during the filtration experimental period, whereas the unmodified membrane showed a sharp flux decline. The best coating conditions of silica nanoparticles resulting in enhanced anti-fouling properties were identified. The biofouling film formation on the membranes was evaluated quantitatively using the flow cytometry method. The results indicated that the modified membranes had 50% lower microbial population growth in terms of total event count compared to the neat membrane. Overall, the experimental results have confirmed that the coating of electrostatically coupled SiO2 nanoparticles and PDOPA (S-NP/PDOPA) on TFC-NF (nanofiltration) membrane surfaces is effective in improving the fouling resistance of the membranes. This result has positive implications for reducing membrane fouling in desalination and industrial wastewater treatment applications.

Insights on Tuning the Nanostructure of rGO Laminate Membranes for Low Pressure Osmosis Process.

In this research, rGO laminates were prepared by a controlled partial reduction step, aimed to avoid aggregation and tune the interlayer spacing (d) between the rGO layers. The mild reducing agent vitamin C (l-AA) and cross-linker poly(carboxylic acid)s were used to improve the stability of the assembled rGO laminate membranes. AFM was used for the first time to further investigate the statistical size distribution of spacing between rGO layers. Topographical images of the edges of the rGO layers were obtained with an AFM instrument; interlayer spacing profiles were extracted, and then the data was plotted and fitted with Gaussian curves. We confirmed that the differently sized spacing coexisted, and their size distribution was affected by the reduction degree of rGO. At greater levels of reduction, more interlayer spacing was formed in the smaller size range, while few large gaps were still present. The obtained rGO laminate composite membranes were evaluated in a low pressure osmosis process such as forward osmosis (FO). The water permeation was higher in the rGO membrane prepared with a medium reduction degree (1.2-R) than the sample prepared by higher reduction degree (2.0-R) due to well-balanced nanochannels in hydrophilic regions and hydrophobic walls for fast transport of water molecules. The solute flux of the FO membrane was inversely correlated to the reduction degree. These findings helped in developing future strategies for designing high water flux and low reverse solute flux rGO membranes that are ideal for an FO process.

Defluoridation of groundwater using aluminum-coated bauxite: Optimization of synthesis process conditions and equilibrium study.

There is no known effective treatment for fluoride-related health disorders, hence prevention through water defluoridation is necessary. This study explored the possibility of modifying the physico-chemical properties of bauxite, a locally available material in many countries including Ghana, by thermal treatment and an aluminum coating, for water defluoridation. The study mainly focused on investigating the effects of varying synthesis process conditions on the defluoridation efficiency of Granular Aluminum Coated Bauxite (GACB). GACB performed better than raw bauxite (RB) and was able to reduce fluoride concentration in groundwater from 5 ± 0.2 mg/L to ≤ 1.5 mg/L, World Health Organization (WHO) guideline. Based on nonlinear Chi-square (χ(2)) analysis, the best-fitting isotherm model for the fluoride-GACB system was in the order: Freundlich > Redlich-Perterson ≈ Langmuir > Temkin. The fluoride adsorption capacity of GACB (qmax = 12.29 mg/g) based on the Langmuir model was found to be either comparable or higher than the capacities of some reported fluoride adsorbents. Aluminum (Al) coating procedures optimized in this study could therefore be a useful approach for synthesizing an effective fluoride adsorbent using bauxite, a locally available material. Kinetic and isotherm analysis, thermodynamic calculations, as well as FTIR and Raman analysis suggested the mechanism of fluoride adsorption onto GACB was complex and involved both physical adsorption and chemisorption processes.

Citrate-Coated Silver Nanoparticles Interactions with Effluent Organic Matter: Influence of Capping Agent and Solution Conditions.

Fate and transport studies of silver nanoparticles (AgNPs) discharged from urban wastewaters containing effluent organic matter (EfOM) into natural waters represent a key knowledge gap. In this study, EfOM interfacial interactions with AgNPs, and their aggregation kinetics were investigated by atomic force microscopy (AFM) and time-resolved dynamic light scattering (TR-DLS), respectively. Two well-characterized EfOM isolates, i.e., wastewater humic (WW humic) and wastewater colloids (WW colloids, a complex mixture of polysaccharides-proteins-lipids), and a River humic isolate of different characteristics were selected. Citrate-coated AgNPs were selected as representative capped-AgNPs. Citrate-coated AgNPs showed a considerable stability in Na(+) solutions. However, Ca(2+) ions induced aggregation by cation bridging between carboxyl groups on citrate. Although the presence of River humic increased the stability of citrate-coated AgNPs in Na(+) solutions due to electrosteric effects, they aggregated in WW humic-containing solutions, indicating the importance of humics characteristics during interactions. Ca(2+) ions increased citrate-coated AgNPs aggregation rates in both humic solutions, suggesting cation bridging between carboxyl groups on their structures as a dominant interacting mechanism. Aggregation of citrate-coated AgNPs in WW colloids solutions was significantly faster than those in both humic solutions. Control experiments in urea solution indicated hydrogen bonding as the main interacting mechanism. During AFM experiments, citrate-coated AgNPs showed higher adhesion to WW humic than to River humic, evidencing a consistency between TR-DLS and AFM results. Ca(2+) ions increased citrate-coated AgNPs adhesion to both humic isolates. Interestingly, strong WW colloids interactions with citrate caused AFM probe contamination (nanoparticles adsorption) even at low Na(+) concentrations, indicating the impact of hydrogen bonding on adhesion. These results suggest the importance of solution conditions and capping agents on the stability of AgNPs in solution. However, the characteristics of organics would play a crucial role in the fate and transport of these nano contaminants in urban wastewaters and natural water systems.

How different is the composition of the fouling layer of wastewater reuse and seawater desalination RO membranes?

To study the effect of water quality and operating parameters on membrane fouling, a comparative analysis of wastewater (WW) and seawater (SW) fouled reverse osmosis (RO) membranes was conducted. Membranes were harvested from SWRO and WWRO pilot plants located in Vilaseca (East Spain), both using ultrafiltration as pretreatment. The SWRO unit was fed with Mediterranean seawater and the WWRO unit was operated using secondary effluent collected from the municipal wastewater treatment plant. Lead and terminal SWRO and WWRO modules were autopsied after five months and three months of operation, respectively. Ultrastructural, chemical, and microbiological analyses of the fouling layers were performed. Results showed that the WWRO train had mainly bio/organic fouling at the lead position element and inorganic fouling at terminal position element, whereas SWRO train had bio/organic fouling at both end position elements. In the case of WWRO membranes, Betaproteobacteria was the major colonizing species; while Ca, S, and P were the major present inorganic elements. The microbial population of SWRO membranes was mainly represented by Alpha and Gammaproteobacteria. Ca, Fe, and S were the main identified inorganic elements of the fouling layer of SWRO membranes. These results confirmed that the RO fouling layer composition is strongly impacted by the source water quality.

Kinetic study of seawater reverse osmosis membrane fouling.

Reverse osmosis (RO) membrane fouling is not a static state but a dynamic phenomenon. The investigation of fouling kinetics and dynamics of change in the composition of the foulant mass is essential to elucidate the mechanism of fouling and foulant-foulant interactions. The aim of this work was to study at a lab scale the fouling process with an emphasis on the changes in the relative composition of foulant material as a function of operating time. Fouled membrane samples were collected at 8 h, and 1, 2, and 4 weeks on a lab-scale RO unit operated in recirculation mode. Foulant characterization was performed by CLSM, AFM, ATR-FTIR, pyrolysis GC-MS, and ICP-MS techniques. Moreover, measurement of active biomass and analysis of microbial diversity were performed by ATP analysis and DNA extraction, followed by pyro-sequencing, respectively. A progressive increase in the abundance of almost all the foulant species was observed, but their relative proportion changed over the age of the fouling layer. Microbial population in all the membrane samples was dominated by specific groups/species belonging to Proteobacteria and Actinobacteria phyla; however, similar to abiotic foulant, their relative abundance also changed with the biofilm age.

Coating of AFM probes with aquatic humic and non-humic NOM to study their adhesion properties.

Atomic force microscopy (AFM) was used to study interaction forces between four Natural Organic Matter (NOM) samples of different physicochemical characteristics and origins and mica surface at a wide range of ionic strength. All NOM samples were strongly adsorbed on positively charged iron oxide-coated silica colloidal probe. Cross-sectioning by focused ion beam milling technique and elemental mapping by energy-filtered transmission electron microscopy indicated coating completeness of the NOM-coated colloidal probes. AFM-generated force-distance curves were analyzed to elucidate the nature and mechanisms of these interacting forces. Electrostatics and steric interactions were important contributors to repulsive forces during approach, although the latter became more influential with increasing ionic strength. Retracting force profiles showed a NOM adhesion behavior on mica consistent with its physicochemical characteristics. Humic-like substances, referred as the least hydrophilic NOM fraction, i.e., so called hydrophobic NOM, poorly adsorbed on hydrophilic mica due to their high content of ionized carboxyl groups and aromatic/hydrophobic character. However, adhesion force increased with increasing ionic strength, suggesting double layer compression. Conversely, polysaccharide-like substances showed high adhesion to mica. Hydrogen-bonding between hydroxyl groups on polysaccharide-like substances and highly electronegative elements on mica was suggested as the main adsorption mechanism, where the adhesion force decreased with increasing ionic strength. Results from this investigation indicated that all NOM samples retained their characteristics after the coating procedure. The experimental approach followed in this study can potentially be extended to investigate interactions between NOM and clean or fouled membranes as a function of NOM physicochemical characteristics and solution chemistry.

Source water quality shaping different fouling scenarios in a full-scale desalination plant at the Red Sea.

The complexity of Reverse Osmosis (RO) membrane fouling phenomenon has been widely studied and several factors influencing it have been reported by many researchers. This original study involves the investigation of two different fouling profiles produced at a seawater RO desalination plant installed on a floating mobile barge. The plant was moved along the coastline of the Red Sea in Saudi Arabia. The two locations where the barge was anchored showed different water quality. At the second location, two modules were harvested. One of the modules was pre-fouled by inorganics during plant operation at the previous site while the other was installed at the second site. Fouled membranes were subjected to a wide range of chemical and microbiological characterization procedures. Drastically different fouling patterns were observed in the two membranes which indicates the influence of source water quality on membrane surface modification and on fouling of RO membranes.