Accessing greater thickness and new morphology features in polyamide active layers of thin-film composite membranes by reducing restrictions in amine monomer supply.

Polyamide formation, via interfacial polymerization (IP) during thin-film composite (TFC) membrane fabrication, is regarded as self-limiting-in the sense that the polyamide film limits its own growth as it forms. During IP, trimesoyl chloride (TMC) and m-phenylenediamine (MPD) react rapidly to form an incipient polyamide film that densifies and slows the diffusion of the more permeable monomer (MPD), thereby limiting polyamide growth and yielding films that typically exhibit thicknesses <350 nm. The morphology of these polyamide films is characterized by a basal layer of void nodular and leaf-like features that is sometimes overlaid by a secondary layer of overlapping flat features. Here, we present evidence showing that polyamide active layers are substantially permeable to MPD, and that minimizing certain restrictions in the MPD supply conditions during IP can result in polyamide active layers of thicknesses several times greater (>1 µm) than those typically reported in the literature. In addition to the basal layer of void nodular features and secondary layer of overlapping flat features that characterize typical polyamide active layers, the thicker films also exhibited three additional morphological features: blanket-like layers atop the basal layer or other void features, multi-layer void structures, and/or void mega-nodules (up to over a micron in diameter). Overall, the results indicate that reducing restrictions in the MPD supply conditions during IP: (1) overcomes the limited polyamide growth observed in conventional TFC membrane fabrication and (2) leads to film morphologies with a more prominent void structure. This latter observation is consistent with recent literature describing the role of CO2 degassing and nanobubble confinement in the development of polyamide active layer morphology. Future studies could vary MPD supply conditions as a new tool to expand the range of achievable thicknesses in active layer casting, regulate active layer morphology and optimize nanobubble confinement conditions independently of MPD supply. Such capabilities could aid in the development of novel supports and TFC structures.

Trends and errors in reverse osmosis membrane performance calculations stemming from test pressure and simplifying assumptions about concentration polarization and solute rejection.

A primary goal in the design of reverse osmosis (RO) membranes is to improve water-solute selectivity and water permeance. These transport properties are commonly calculated in the literature using the solution-diffusion model with selectivity (A/B, bar-1) defined as the ratio between water permeance (A, L.m-2.h-1.bar-1) and solute permeance (B, L.m-2.h-1). In calculating transport properties, researchers often use simplifying assumptions about concentration polarization (CP; i.e., assuming negligible CP or a certain extent of CP) and solute rejection (i.e., assuming solute rejection is approximately 1 to enable the explicit use of the CP modulus in solute permeance calculations). Although using these assumptions to calculate transport properties is common practice, we could not find a study that evaluated the errors associated with using them. The uncertainty in these errors could impede unequivocally identifying manufacturing approaches that break through the commonly plotted trade-off frontier between selectivity and water permeance (A/B vs. A); however, we did not find in the literature a study that quantified such errors. Accordingly, we aimed to: (1) quantify the error in transport properties (A, B, and A/B) calculated using common simplifying assumptions about CP and rejection; and (2) determine if using simplifying assumptions affects conclusions drawn about membrane performance or trends concerning the trade-off frontier. Results show that compared with the case where no simplifying assumptions were made, simplified calculations were least accurate at low pressures for water permeance (up to 78% overestimation) and high pressures for solute permeance (up to 188% overestimation). Accordingly, the corresponding selectivities were least accurate at low pressure (up to 111% overestimation) and high pressure (up to 66% underestimation), and conclusions drawn about membrane performance and trade-off trends were pressure-dependent. Importantly, even in the absence of simplifying assumptions, selectivity results were pressure-dependent, indicating the importance of standardizing test conditions for the continued use of current performance metrics (i.e., A/B and A). We propose a two-pressure approach-collecting data for A and B at a high and a low pressure, respectively-combined with simplifying assumptions for more accurate simplified estimations of selectivity (< 10% absolute error). Our work contributes to a better understanding of the effects of operating pressure and key simplifying assumptions commonly used in calculating RO membrane performance metrics and interpretation of corresponding results.

Effect of Feed Water pH on the Partitioning of Alkali Metal Salts from Aqueous Phase into the Polyamide Active Layers of Reverse Osmosis Membranes.

The partitioning of solutes into the polyamide active layers of reverse osmosis (RO) membranes is a key membrane property determining solute permeation. Quantification of partition coefficients and their dependence on feedwater pH would contribute to the development of predictive transport models of contaminant transport through RO membranes; however, neither solute partitioning nor the effect of feed solution pH on partitioning has been thoroughly characterized in the literature. Accordingly, we characterized the partitioning of all chloride salts of alkali metals (CsCl, RbCl, KCl, NaCl, and LiCl) from the aqueous phase into the polyamide active layers of five polyamide RO membranes, including one prepared in-house and four commercial membranes. We evaluated the effect of pH on the partitioning of alkali metal salts and whether the effect of pH on salt partitioning and rejection is consistent with Donnan theory predictions. Results showed that for all membranes, the partition coefficients of all salts were less than one and did not differ substantially among RO membranes. Results also indicated that for all membranes tested, Donnan theory provided an appropriate theoretical framework to estimate the effect of pH on salt partitioning (evaluated for all chloride salts of alkali metals) and salt rejection (evaluated for NaCl). Thus, we conclude that changes in salt rejection resulting from feed solution pH are primarily driven by changes in salt partitioning with comparatively small changes in salt diffusion coefficients.

2-Aminoimidazole Reduces Fouling and Improves Membrane Performance.

Biofouling is difficult to control and hinders the performance of membranes in all applications but is of particular concern when natural waters are purified. Fouling, via multiple mechanisms (organic-only, biofouling-only, cell-deposition-only, and organic+biofouling), of a commercially available membrane (control) and a corresponding membrane coated with an anti-biofouling 2-aminoimidazole (2-AI membrane) was monitored and characterized during the purification of a natural water. Results show that the amount of bacterial cell deposition and organic fouling was not significantly different between control and 2-AI membranes; however, biofilm formation, concurrent or not with other fouling mechanisms, was significantly inhibited (95-98%, p<0.001) by the 2-AI membrane. The limited biofilm that formed on the 2-AI membrane was weaker (as indicated by the polysaccharide to protein ratio) and thus presumably easier to remove. The conductivity rejection by the 2-AI and control membranes was not significantly different throughout the 75-hour experiments, but the rejection of dissolved organic carbon by biofouled (biofouling-only, cell-deposition-only, and organic+biofouling) 2-AI membranes was statistically higher (10-12%, p=0.003-0.07). When biofouled, the water permeance of the 2-AI membranes decreased significantly less (p<0.05) over 75 hours than that of the control membranes, whether or not other additional types of fouling occurred concurrently. Despite the initially lower water permeances of 2-AI membranes (11% lower on average than controls), the 2-AI membranes outperformed the controls (10-11% higher average water permeance) after biofilm formation occurred. Overall, 2-AI membranes fouled less than controls without detriment to water productivity and solute rejection.

Predictive Analysis Using Chemical-Gene Interaction Networks Consistent with Observed Endocrine Activity and Mutagenicity of U.S. Streams.

In a recent U.S. Geological Survey/U.S. Environmental Protection Agency study assessing more than 700 organic compounds in 38 streams, in vitro assays indicated generally low estrogen, androgen, and glucocorticoid receptor activities, with 13 surface waters with 17ß-estradiol-equivalent (E2Eq) activities greater than a 1-ng/L estimated effects-based trigger value for estrogenic effects in male fish. Among the 36 samples assayed for mutagenicity in the Salmonella bioassay (reported here), 25% had low mutagenic activity and 75% were not mutagenic. Endocrine and mutagenic activities of the water samples were well correlated with each other and with the total number and cumulative concentrations of detected chemical contaminants. To test the predictive utility of knowledge-base-leveraging approaches, site-specific predicted chemical-gene (pCGA) and predicted analogous pathway-linked (pPLA) association networks identified in the Comparative Toxicogenomics Database were compared with observed endocrine/mutagenic bioactivities. We evaluated pCGA/pPLA patterns among sites by cluster analysis and principal component analysis and grouped the pPLA into broad mode-of-action classes. Measured E2eq and mutagenic activities correlated well with predicted pathways. The pPLA analysis also revealed correlations with signaling, metabolic, and regulatory groups, suggesting that other effects pathways may be associated with chemical contaminants in these waters and indicating the need for broader bioassay coverage to assess potential adverse impacts.

Chlorination of Source Water Containing Iodinated X-ray Contrast Media: Mutagenicity and Identification of New Iodinated Disinfection Byproducts.

Iodinated contrast media (ICM) are nonmutagenic agents administered for X-ray imaging of soft tissues. ICM can reach µg/L levels in surface waters because they are administered in high doses, excreted largely unmetabolized, and poorly removed by wastewater treatment. Iodinated disinfection byproducts (I-DBPs) are highly genotoxic and have been reported in disinfected waters containing ICM. We assessed the mutagenicity in Salmonella of extracts of chlorinated source water containing one of four ICM (iopamidol, iopromide, iohexol, and diatrizoate). We quantified 21 regulated and nonregulated DBPs and 11 target I-DBPs and conducted a nontarget, comprehensive broad-screen identification of I-DBPs. We detected one new iodomethane (trichloroiodomethane), three new iodoacids (dichloroiodoacetic acid, chlorodiiodoacetic acid, bromochloroiodoacetic acid), and two new nitrogenous I-DBPs (iodoacetonitrile and chloroiodoacetonitrile). Their formation depended on the presence of iopamidol as the iodine source; identities were confirmed with authentic standards when available. This is the first identification in simulated drinking water of chloroiodoacetonitrile and iodoacetonitrile, the latter of which is highly cytotoxic and genotoxic in mammalian cells. Iopamidol (5 µM) altered the concentrations and relative distribution of several DBP classes, increasing total haloacetonitriles by >10-fold. Chlorination of ICM-containing source water increased I-DBP concentrations but not mutagenicity, indicating that such I-DBPs were either not mutagenic or at concentrations too low to affect mutagenicity.

Dataset of reverse osmosis membrane transport properties calculated with and without assumptions about concentration polarization and solute rejection and the errors associated with each assumption.

The data shared in this work represent aspects of the performance of reverse osmosis membranes during filtration. We present pressure, permeate flux, and solute rejection data gathered during cross-flow filtration experiments, which were used to (i) model water and solute permeation through the membranes and (ii) calculate concentration polarization moduli and a suite of transport properties, including water permeance, solute permeance, and water-solute selectivity. Membrane transport properties were calculated with the different approaches commonly used to simplify transport property calculations. Typical calculations of these transport properties often use simplifying assumptions (e.g., negligible concentration polarization and solute rejection close to 100%). However, the extent of the errors associated with using simplifying assumptions in this context were not previously known or quantified. This publication and corresponding dataset pertain to figures presented in the accompanying work (Armstrong et al., 2022) [1].

Assessing the skin irritation and sensitizing potential of concentrates of water chlorinated in the presence of iodinated X-ray contrast media.

Chemical disinfection of water provides significant public health benefits. However, disinfectants like chlorine can react with naturally occurring materials in the water to form disinfection byproducts (DBPs). Natural levels of iodine have been reported to be too low in some source waters to account for the levels of iodinated DBPs detected. Iodinated X-ray contrast media (ICM) have been identified as a potential source of iodine. The toxicological impact of ICM present in source water at the time of disinfection has not been fully investigated. Iopamidol, iohexol, iopromide, and diatrizoate are among the ICM most frequently detected in water. In this study, source water containing one of these four ICM was chlorinated; non-chlorinated ICM-containing water samples served as controls. Reactions were conducted at an ICM concentration of 5 µM and a chlorine dose of 100 µM over 72 hr. Water concentrates (20,000-fold) were prepared by XAD-resin/ethyl acetate extraction and DMSO solvent exchange. We used the MatTek® reconstituted human epithelial skin irritation model to evaluate the water concentrates and also assessed the dermal irritation and sensitization potential of these concentrates using the LLNA:BrdU ELISA in BALB/c mice. None of the water concentrates tested (2500X) resulted in a skin irritant response in the MatTek® skin irritation model. Likewise, none of the concentrates (2500X, 1250X, 625X, 312.5X, 156.25X) produced a skin irritation response in mice: erythema was minimal; the maximum increase in ear thickness was less than 25%. Importantly, none of the concentrates produced a positive threshold response for allergic skin sensitization at any concentration tested in the LLNA:BrdU ELISA. We conclude that concentrates of water disinfected in the presence of four different ICM did not cause significant skin irritation or effects consistent with skin sensitization at the concentrations tested.