Orlando Coronell

Depth Heterogeneity of Fully Aromatic Polyamide Active Layers in Reverse Osmosis and Nanofiltration Membranes

We studied the depth heterogeneity of fully aromatic polyamide (PA) active layers in commercial reverse osmosis (RO) and nanofiltration (NF) membranes by quantifying near-surface (i.e., top 6 nm) and volume-averaged properties of the active layers using X-ray photoelectron spectrometry (XPS) and Rutherford backscattering spectrometry (RBS), respectively. Some membranes (e.g., ESPA3 RO) had active layers that were depth homogeneous with respect to the concentration and pK(a) distribution of carboxylic groups, degree of polymer cross-linking, concentration of barium ion probe that associated with ionized carboxylic groups, and steric effects experienced by barium ion. Other membranes (e.g., NF90 NF) had active layers that were depth heterogeneous with respect to the same properties. Our results therefore support the existence of both depth-homogeneous and depth-heterogeneous active layers. It remains to be assessed whether the depth heterogeneity consists of gradually changing properties throughout the active layer depth or of distinct sublayers with different properties.

Ionization behavior, stoichiometry of association, and accessibility of functional groups in the active layers of reverse osmosis and nanofiltration membranes.

We characterized the fully aromatic polyamide (PA) active layers of six commercial reverse osmosis (RO) and nanofiltration (NF) membranes and found that in contrast to their similar elemental composition, total concentration of functional groups, and degree of polymerization, the ionization behavior and spatial distribution of carboxylic (R-COOH) groups within the active layers can be significantly different. We also studied the steric effects experienced by barium ion (Ba2+) in the active layers by determining the fraction of carboxylate (R-COO-) groups accessible to Ba2+; such fraction, referred to as the accessibility ratio (AR), was found to vary within the range AR=0.40-0.81, and to be generally independent of external solution pH. Additionally, we studied an NF membrane with a sulfonated polyethersulfone (SPES) active layer, and found that the concentration of sulfonate (R-SO3-) groups in the active layer was 1.67 M, independent of external solution pH and approximately three times higher than the maximum concentration (approximately 0.45+/-0.25 M) of R-COO- groups in PA active layers. The R-SO3- groups were found to be highly accessible to Ba2+ (AR=0.95+/-0.01).

Partitioning of salt ions in FT30 reverse osmosis membranes

FT30 membranes consist of a polyamide active layer interfacially polymerized on a porous polysulfone support. The ion partition coefficient κ in the active layer is a key thermodynamic parameter that partially controls the ability of the membrane to desalinate water. Membranes are soaked in aqueous solutions of CsCl, KBr, or Na2WO4 with salt concentrations of 0.002M<Cs<2M, freeze dried to remove water without disturbing ion distribution, and analyzed by Rutherford backscattering spectrometry. For Cs<0.01M, κ is surprisingly large and independent of Cs, κ=6±2. The porosity ϕ of the top 500nm of the support layer is also extracted from the RBS data: ϕ=0.45±0.05.

Bulk chlorine uptake by polyamide active layers of thin-film composite membranes upon exposure to free chlorine-kinetics, mechanisms, and modeling.

We studied the volume-averaged chlorine (Cl) uptake into the bulk region of the aromatic polyamide active layer of a reverse osmosis membrane upon exposure to free chlorine. Volume-averaged measurements were obtained using Rutherford backscattering spectrometry with samples prepared at a range of free chlorine concentrations, exposure times, and mixing, rinsing, and pH conditions. Our volume-averaged measurements complement previous studies that have quantified Cl uptake at the active layer surface (top ≈ 7 nm) and advance the mechanistic understanding of Cl uptake by aromatic polyamide active layers. Our results show that surface Cl uptake is representative of and underestimates volume-averaged Cl uptake under acidic conditions and alkaline conditions, respectively. Our results also support that (i) under acidic conditions, N-chlorination followed by Orton rearrangement is the dominant Cl uptake mechanism with N-chlorination as the rate-limiting step; (ii) under alkaline conditions, N-chlorination and dechlorination of N-chlorinated amide links by hydroxyl ion are the two dominant processes; and (iii) under neutral pH conditions, the rates of N-chlorination and Orton rearrangement are comparable. We propose a kinetic model that satisfactorily describes Cl uptake under acidic and alkaline conditions, with the largest discrepancies between model and experiment occurring under alkaline conditions at relatively high chlorine exposures.

Amide Link Scission in the Polyamide Active Layers of Thin-Film Composite Membranes upon Exposure to Free Chlorine: Kinetics and Mechanisms

The volume-averaged amide link scission in the aromatic polyamide active layer of a reverse osmosis membrane upon exposure to free chlorine was quantified at a variety of free chlorine exposure times, concentrations, and pH and rinsing conditions. The results showed that (i) hydroxyl ions are needed for scission to occur, (ii) hydroxide-induced amide link scission is a strong function of exposure to hypochlorous acid, (iii) the ratio between amide links broken and chlorine atoms taken up increased with the chlorination pH and reached a maximum of ∼25%, (iv) polyamide disintegration occurs when high free chlorine concentrations, alkaline conditions, and high exposure times are combined, (v) amide link scission promotes further chlorine uptake, and (vi) scission at the membrane surface is unrepresentative of volume-averaged scission in the active layer. Our observations are consistent with previously proposed mechanisms describing amide link scission as a result of the hydrolysis of the N-chlorinated amidic N-C bond due to nucleophilic attack by hydroxyl ions. This study increases the understanding of the physicochemical changes that could occur for membranes in treatment plants using chlorine as an upstream disinfectant and the extent and rate at which those changes would occur.

Relationship between performance deterioration of a polyamide reverse osmosis membrane used in a seawater desalination plant and changes in its physicochemical properties.

While it is known that the performance of reverse osmosis membranes is dependent on their physicochemical properties, the existing literature studying membranes used in treatment facilities generally focuses on foulant layers or performance changes due to fouling, not on the performance and physicochemical changes that occur to the membranes themselves. In this study, the performance and physicochemical properties of a polyamide reverse osmosis membrane used for three years in a seawater desalination plant were compared to those of a corresponding unused membrane. The relationship between performance changes during long-term use and changes in physicochemical properties was evaluated. The results showed that membrane performance deterioration (i.e., reduced water flux, reduced contaminant rejection, and increased fouling propensity) occurred as a result of membrane use in the desalination facility, and that the main physicochemical changes responsible for performance deterioration were reduction in PVA coating coverage and bromine uptake by polyamide. The latter was likely promoted by oxidant residual in the membrane feed water. Our findings indicate that the optimization of membrane materials and processes towards maximizing the stability of the PVA coating and ensuring complete removal of oxidants in feed waters would minimize membrane performance deterioration in water purification facilities.

Minimization of short-term low-pressure membrane fouling using a magnetic ion exchange (MIEX®) resin

Two challenges to low-pressure membrane (LPM) filtration are limited rejection of dissolved organic matter (DOM) and membrane fouling by DOM. The magnetic ion exchange resin MIEX(®) (Ixom Watercare Inc.) has been demonstrated to remove substantial amounts of DOM from many source waters, suggesting that MIEX can both reduce DOM content in membrane feed waters and minimize LPM fouling. We tested the effect of MIEX pretreatment on the reduction of short-term LPM fouling potential using feed waters varying in DOM concentration and composition. Four natural and two synthetic waters were studied and a polyvinylidene fluoride (PVDF) hollow-fiber ultrafiltration membrane was used in membrane fouling tests. To evaluate whether MIEX removes the fractions of DOM that cause LPM fouling, the DOM in raw, MIEX-treated, and membrane feed and backwash waters was characterized in terms of DOM concentration and composition. Results showed that: (i) the efficacy of MIEX to reduce LPM fouling varies broadly with source water; (ii) MIEX preferentially removes terrestrial DOM over microbial DOM; (iii) microbial DOM is a more important contributor to LPM fouling than terrestrial DOM, relative to their respective concentrations in source waters; and (iv) the fluorescence intensity of microbial DOM in source waters can be used as a quantitative indicator of the ability of MIEX to reduce their membrane fouling potential. Thus, when ion exchange resin processes are used for DOM removal towards membrane fouling reduction, it is advisable to use a resin that has been designed to effectively remove microbial DOM.

Junction Potentials Bias Measurements of Ion Exchange Membrane Permselectivity

Ion exchange membranes (IEMs) are versatile materials relevant to a variety of water and waste treatment, energy production, and industrial separation processes. The defining characteristic of IEMs is their ability to selectively allow positive or negative ions to permeate, which is referred to as permselectivity. Measured values of permselectivity that equal unity (corresponding to a perfectly selective membrane) or exceed unity (theoretically impossible) have been reported for cation exchange membranes (CEMs). Such nonphysical results call into question our ability to correctly measure this crucial membrane property. Because weighing errors, temperature, and measurement uncertainty have been shown to not explain these anomalous permselectivity results, we hypothesized that a possible explanation are junction potentials that occur at the tips of reference electrodes. In this work, we tested this hypothesis by comparing permselectivity values obtained from bare Ag/AgCl wire electrodes (which have no junction) to values obtained from single-junction reference electrodes containing two different electrolytes. We show that permselectivity values obtained using reference electrodes with junctions were greater than unity for CEMs. In contrast, electrodes without junctions always produced permselectivities lower than unity. Electrodes with junctions also resulted in artificially low permselectivity values for AEMs compared to electrodes without junctions. Thus, we conclude that junctions in reference electrodes introduce two biases into results in the IEM literature: (i) permselectivity values larger than unity for CEMs and (ii) lower permselectivity values for AEMs compared to those for CEMs. These biases can be avoided by using electrodes without a junction.

Partitioning of Alkali Metal Salts and Boric Acid from Aqueous Phase into the Polyamide Active Layers of Reverse Osmosis Membranes

The partition coefficient of solutes into the polyamide active layer of reverse osmosis (RO) membranes is one of the three membrane properties (together with solute diffusion coefficient and active layer thickness) that determine solute permeation. However, no well-established method exists to measure solute partition coefficients into polyamide active layers. Further, the few studies that measured partition coefficients for inorganic salts report values significantly higher than one (∼3-8), which is contrary to expectations from Donnan theory and the observed high rejection of salts. As such, we developed a benchtop method to determine solute partition coefficients into the polyamide active layers of RO membranes. The method uses a quartz crystal microbalance (QCM) to measure the change in the mass of the active layer caused by the uptake of the partitioned solutes. The method was evaluated using several inorganic salts (alkali metal salts of chloride) and a weak acid of common concern in water desalination (boric acid). All partition coefficients were found to be lower than 1, in general agreement with expectations from Donnan theory. Results reported in this study advance the fundamental understanding of contaminant transport through RO membranes, and can be used in future studies to decouple the contributions of contaminant partitioning and diffusion to contaminant permeation.

Microstructure determines water and salt permeation in commercial ion exchange membranes

Ion-exchange membrane (IEM) performance in electrochemical processes such as fuel cells, redox flow batteries, or reverse electrodialysis (RED) is typically quantified through membrane selectivity and conductivity, which together determine the energy efficiency. However, water and co-ion transport (i.e., osmosis and salt diffusion/fuel crossover) also impact energy efficiency by allowing uncontrolled mixing of the electrolyte solutions to occur. For example, in RED with hypersaline water sources, uncontrolled mixing consumes 20-50% of the available mixing energy. Thus, in addition to high selectivity and high conductivity, it is desirable for IEMs to have low permeability to water and salt to minimize energy losses. Unfortunately, there is very little quantitative water and salt permeability information available for commercial IEMs, making it difficult to select the best membrane for a particular application. Accordingly, we measured the water and salt transport properties of 20 commercial IEMs and analyzed the relationships between permeability, diffusion, and partitioning according to the solution-diffusion model. We found that water and salt permeance vary over several orders of magnitude among commercial IEMs, making some membranes better suited than others to electrochemical processes that involve high salt concentrations and/or concentration gradients. Water and salt diffusion coefficients were found to be the principal factors contributing to the differences in permeance among commercial IEMs. We also observed that water and salt permeability were highly correlated to one another for all IEMs studied, regardless of polymer type or reinforcement. This finding suggests that transport of mobile salt in IEMs is governed by the microstructure of the membrane and provides clear evidence that mobile salt does not interact strongly with polymer chains in highly swollen IEMs.