Removal of strontium by nanofiltration: Role of complexation and speciation of strontium with organic matter.

Strontium (Sr) removal from water is required because excessive naturally occurring Sr exposure is hazardous to human health. Climate and seasonal changes cause water quality variations, in particular quality and quantity of organic matter (OM) and pH, and such variations affect Sr removal by nanofiltration (NF). The mechanisms for such variations are not clear and thus OM complexation and speciation require attention. Sr removal by NF was investigated with emphasis on the role of OM (type and concentration) and pH (2-12) on possible removal mechanisms, specifically size and/or charge exclusion as well as solute-solute interactions. The filtration results show that the addition of various OM (10 types) and an increase of OM concentration (2-100 mgC.L-1) increased Sr removal by 10-15%. The Sr-OM interaction was enhanced with increasing OM concentration, implying enhanced size exclusion via Sr-OM interaction as the main mechanism. Such interactions were quantified by asymmetric flow field-flow fractionation (FFFF) coupled with an inductively coupled plasma mass spectrometer (ICP-MS). Both extremely low and high pH increased Sr removal due to the enhanced charge exclusion and Sr-OM interactions. This work elucidated and verified the mechanism of OM and pH on Sr removal by NF membranes.

Organic micropollutant removal and phosphate recovery by polyelectrolyte multilayer membranes: Impact of buildup interactions.

Polyelectrolyte multilayer (PEM) deposition conditions can favorably or adversely affect the membrane filtration performance of various pollutants. Although pH and ionic strength have been proven to alter the characteristics of PEM, their role in determining the buildup interactions that control filtration efficacy has not yet been conclusively proved. A PEM constructed using electrostatic or non-electrostatic interactions from controlled deposition of a weak polyelectrolyte could retain both charged and uncharged pollutants from water. The fundamental relationship between polyelectrolyte charge density, PEM buildup interaction, and filtration performance was explored using a weak-strong electrolyte pair consisting of branching poly (ethyleneimine) and poly (styrene sulfonate) (PSS) across pH ranges of 4-10 and NaCl concentrations of 0 M-0.5 M. PEI/PSS multilayers at acidic pH were dominated by electrostatic interactions, which favored the selective removal of a charged solute, phosphate over chloride, while at alkaline pH, non-electrostatic interactions dominated, which favored the removal of oxybenzone (OXY), a neutral hydrophobic solute. The key factor determining these interactions was the charge density of PEI, which is controlled by pH and ionic strength of the deposition solutions. These findings indicate that the control of buildup interactions can largely influence the physico-chemical and transport characteristics of PEM membranes.

Spectro-kinetic investigations on the release mechanism of lysozyme from layer-by-layer reservoirs.

The investigations of protein adsorption and release on interfaces aid in the elucidation of the protein-surface interaction mechanism, which has several applications in the biomedical area. The spectro-kinetic and morphological analysis of the release of lysozyme (Lyz) from chitosan/polystyrene sulphonate (CHI/PSS) multilayer immobilized at pHs 10.6, 8.8 and 5.0 shows that the extent of release strongly depends on the pH of Lyz loading and the ionic strength of the desorbing solution. When compared to pH 8.8, the release for pH 10.6 achieves equilibrium more rapidly. At loading pH 10.6, the release is surface-mediated, at pH 8.8, it is both surface- and bulk-mediated, while at pH 5.0 it is bulk mediated with minimal release. Lyz released for loading pH 10.6 retains its native secondary structure. Kinetic fitting suggests that high loading pH 8.8-10.6 and high release ionic strength (0.5-1.0 M NaCl) lead to burst release of Lyz from CHI/PSS multilayer. Surface morphology changes of multilayer interface upon Lyz loading and release are highlighted by SEM topography and AFM height distribution analysis. The present work indicates that CHI/PSS multilayer system can function as a reservoir for burst as well as controlled release of lysozyme by selecting the loading pH and ionic strength.

Membrane-organic solute interactions in asymmetric flow field flow fractionation: Interplay of hydrodynamic and electrostatic forces.

The structure and size characterization of organic matter (OM) using flow field-flow fractionation (FFFF) is interesting due to the numerous interactions of OM in aquatic systems and water treatment processes. The estimation of hydrodynamic and electrostatic forces involved in the fractionation of OM over different molecular weight cut-off (MWCO) membranes is vital for a better understanding of the FFFF process. This work aims to understand the membrane-OM interactive forces with respect to membrane MWCO, solute molecular weight, flow rates, solution pH and ionic strength. Polystyrene sulfonate sodium salt (PSS) of molecular weights 10, 30 and 65 kDa were used as model organic solutes for fractionation over ultrafiltration (UF) membranes of MWCO 1-30 kDa. Maximum fractionation of PSS was achieved by using a tight membrane of 1 kDa MWCO at the conditions of high permeate flow rate (1.5-2.0 mL·min-1), low concentrate flow rate (0.2-0.3 mL·min-1) and low ionic strength (10 mM). The better fractionation corresponds to high permeate drag force and low concentrate drag force. A low membrane-solute DLVO interaction is favourable for the retention of a small solute. This study illustrated that FFFF characteristics can be analyzed based on membrane-solute interactive forces controlled by selected flow, size and charge parameters.

Renewable energy powered membrane technology: Implications of adhesive interaction between membrane and organic matter on spontaneous osmotic backwash cleaning.

Organic matter (OM) in surface and ground waters may cause membrane fouling that is laborious to clean once established. Spontaneous osmotic backwash (OB) induced by solar irradiance fluctuation has been demonstrated for early mineral scaling/organic fouling control in decentralised small-scale photovoltaic powered-nanofiltration/reverse osmosis (PV-NF/RO) membrane systems. However, various OM types will interact differently with membranes which in turn affects the effectiveness of OB. This work evaluates the suitability of spontaneous OB cleaning for eleven OM types (covering low-molecular-weight organics (LMWO), humic substances, polyphenolic compounds and biopolymers) regarding adhesive interactions with NF/RO membranes. The adhesive interactions were quantified by an asymmetric flow field-flow fractionation coupled with an organic carbon detector (FFFF-OCD). The underlying mechanism of OM-membrane adhesive interactions affecting OB cleaning was elucidated. The results indicate that humic acid (a typical humic substance) and tannic acid (a typical polyphenolic compound) induced stronger adhesive interaction with NF/RO membranes than biopolymers and LMWO. When the mass loss of an OM due to adhesion was below a critical range, the spontaneous OB is most effective (>85% flux recovery); and above this range, the OB becomes ineffective (<50% flux recovery). Polyphenolic compounds and humic substances resulted in lower OB cleaning efficiency, due to their higher aromatic content, enhancing hydrophobic interactions and hydrogen bonding. Calcium-facilitated adhesion of some OM types (such as humic substances, polyphenolics and biopolymers) increased irreversible organic fouling potential and weakened OB cleaning, which was verified by both FFFF-OCD and membrane filtration results. This work provides a guidance to formulate strategies to enhance spontaneous OB cleaning, such as first identifying the adhesion of OM in feedwater (surface and ground waters) using FFFF-OCD, and then removing "sticky" OM using suitable pre-treatment processes.

Removal of arsenic(III) via nanofiltration: contribution of organic matter interactions.

The removal of arsenic(III) (As(III)) with nanofiltration (NF) was investigated with emphasis on the role of salinity, pH and organic matter on retention mechanisms. While no measurable impact of salinity on As(III) retention with NF membranes (NF270 and NF90) was observed, a significant increase in As(III) retention occurred from pH 9 to pH 12. This was explained by As(III) deprotonation at pH > 9 that enhanced Donnan (charge) exclusion. Of the five different organic matter types investigated at 10 mgC/L, only humic acid (HA) increased As(III) retention by up to 10%. Increasing HA concentration to 100 mgC/L enhanced As(III) retention by 40%, which was attributed to As(III)-HA complexation. Complexation was confirmed by field-flow fractionation inductively coupled plasma mass spectrometry (FFF-ICP-MS) measurements, which showed that the bound As(III) increased with HA concentration. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) showed that NF90, which exhibited lower permeability reduction than NF270, has accumulated a lower amount of As(III) in the presence of HA, where As(III)-HA complex was formed in the feed solution. This finding implies that As(III) retention with NF technology can be enhanced by complexation, instead of using other methods such as oxidation or pH adjustement.

Low - cost multilayered green fiber for the treatment of textile industry waste water.

Layer by layer (LbL) assembly can be regarded as an emerging technology for the separation of organic micro-pollutants from water. Direct assembly of polyelectrolytes (PEs) under LbL mode on natural support material is rare. Here we report the integration of LbL to one of the most resourceful support materials that might have an enduring impact on water treatment in color industry. A low-cost adsorbent is developed from chitosan (CHI) and polyacrylic acid (PAA) through LbL deposition on coir fiber (CF) by alternate exposure to their aqueous solutions. Their layer dependent formation is characterized by spectroscopic and microscopic techniques. CHI/PAA multilayer coated coir fiber or simply, layered coir fiber (LCF) showed high loading of cationic and anionic dyes both at acidic and alkaline loading pH. The loading was between 70% and 99% at the acidic pH 3 which is attributed to the binding between LCF and dye molecules by electrostatic and hydrophobic forces. The performance of LCF in presence of NaCl, Na2SO4 and sodium dodecyl sulfate (SDS) in dye solution is discussed. Textile industrial waste water showed significant reduction in dye (81%) content along with COD (84%) and TDS.

Sustainable polyelectrolyte multilayer surfaces: possible matrix for salt/dye separation.

The development of a sustainable membrane surface based on chitosan/poly(acrylic acid) (CHI/PAA) multilayers suitable for applications in analytical separations is reported here. Bilayers are constructed on polyamide microfiltration membranes at a pH combination of 3/3 (CHI pH/PAA pH) through a layer by layer approach. A 12.5 bilayer yielded a thickness of 400 nm. Low pressure (10 psi) filtrations through a 5.5 bilayered membrane exhibited high flux (7 m(3) m(-2) day(-1)) and selectivity (NaCl/reactive black 5 (RB5) selectivity >8000). The selectivity and flux observed here are the highest reported to date for low pressure filtrations through membranes. The increase in flux with increasing feed salt concentration is correlated with morphological transformations. Salt content above 7500 ppm causes some perturbation of surface layers. The presence of RB5, a model dye in the feed, restores the surface to maintain sustainability. A skin layer as thin as 50 nm imparts a large separation window. An RB5 feed concentration of 500 ppm results in 98.64% rejection with a flux of 25.79 m(3) m(-2) day(-1). The increase in flux with feed dye concentration supports the plasticizing action of RB5. The transport studies with large feed dye concentrations indicate that at a dye concentration of 500 ppm, the linear growing region (pre-exponential, 5.5 bilayer) itself provides a separation window similar to that of 100 ppm. At the same time, 1000 ppm requires a 9.5 bilayer that falls in the nonlinear growing region. Scanning electron microscopy images show the increase in porosity with respect to feed dye. Interesting morphologies that show the sustainable nature of the membrane surfaces along with the transport data of RB5 are presented.