Simplified analysis of contaminant rejection during ground- and surface water nanofiltration under the information collection rule

A simple, closed-form analytical expression based on the homogenous solution diffusion model is derived for contaminant removal during nanofiltration (NF) of ground and surface water. Solute permeation and back-diffusion coefficients were used as fitting parameters to model rejection characteristics of four thin-film composite NF membranes under conditions typical of drinking water NF. Nonlinear fits of the model to experimental data suggests that the United States Environmental Protection Agency's (USEPA)'s Information Collection Rule protocol for bench-scale studies could be improved to obtain greater precision of the mass transfer coefficients. The model was found to fit rejection data for several water treatment contaminants including total organic carbon, precursors to total organic halide, four trihalomethanes and nine haloacetic acids containing chlorine and bromine, calcium and total hardness, alkalinity and conductivity. The simplified approach to mass transfer calculations from multisolute systems suggests that feed water recovery has a stronger influence on contaminant rejection than permeate flux. Evidence for coupled transport of divalent inorganic ions is also presented. Even though the model developed does not account for ion coupling and cannot be applied in a purely predictive mode, it can assist in the better design and interpretation of data obtained from site-specific pilot-scale water treatment NF studies conducted in support of plant design.     

Spontaneous programmed cell death in infiltrating duct carcinoma: association with p53, BCL-2, hormone receptors and tumor proliferation

Recent evidence has emphasized the importance of programmed cell death or apoptosis in the maintenance of tissue homeostasis and pathogenesis of tumors. This study, analyzed in breast cancer, investigates the significance of apoptosis in relation to the expression of p53 and bcl-2 proteins, tissue proliferation defined by Ki-67 expression, hormone receptors and tumor grade. The extent of apoptosis was defined by morphological criteria and the TUNEL (Tdt-mediated dUTP biotin nick end labelling) assay. Immunocytochemistry was performed for p53, bcl-2, estrogen receptor, progesterone receptor and Ki-67 expression. Mutant p53 protein was detected using a mutant specific ELISA. Immunoreactivity of p53 significantly correlated with the presence of mutant p53 protein detected by ELISA (r = 0.654, p = 0.00001). An inverse correlation was observed between bcl-2 expression and the extent of apoptosis (r = -0.33369, p = 0.01912). The extent of apoptosis directly correlated with p53 protein accumulation (r = 0.485, p = 0.00041), Ki-67 immunoreactivity (r = 0.435, p = 0.001), histopathological grade (r = 0.492, p = 0.0003), tumor size (r = 0.326, p = 0.023) and lymph node status (r = 0.287, p = 0.047). A direct correlation was also observed between p53 expression and Ki-67 immunoreactivity (r = 0.623, p = 0.0002). There was no statistically significant association between estrogen and progesterone receptor status and apoptosis. In addition, the TNM stage of the disease correlated with immunoreactivity of p53 (r = 0.572, p = 0.00012) and Ki-67 (r = 0.3744, p = 0.00818). Bcl-2, by inhibiting apoptosis, may cause a shift in tissue kinetics towards the preservation of genetically aberrant cells, thereby facilitating tumor progression. These results imply that rapidly proliferating tumors appear to have a high "cell turnover state" in which there may be an increased chance of apoptosis amongst the proliferating cells. The ability of apoptosis to also occur in the presence of mutant p53 protein suggests the existence of at least two p53-dependent apoptotic pathways, one requiring activation of specific target genes and the other independent of it.     

Virus removal by iron coagulation-microfiltration

This study was undertaken to determine virus removal efficiency by iron coagulation followed by microfiltration (MF) in water treatment using the MS2 bacteriophage (25 nm diameter) as a tracer virus. Results from these bench-scale studies were used to propose a mechanism for virus removal by iron coagulation–MF. Ferric chloride was used as coagulant, and the dosages were 0, 2, 5, and 10 mg/L as Fe(III) with pH adjusted during mixing to 6.3, 7.3 and 8.3. In the absence of iron-coagulation and with less than 2 mg/L Fe, MF alone achieved less than a 0.5 log removal of MS2 virus. However, iron-coagulation pretreatment dramatically improved virus removal, especially in the 5–10 mg/L Fe dose range, ultimately achieving more than 4-log removal at pH 6.3 with 10-mg/L Fe dose. For the 5 and 10 mg/L Fe dosages, decreasing pH in the 8.3–6.3 range resulted in significantly greater virus removal. For 0 and 2 mg/L iron dosages, decreasing pH in the 8.3–6.3 range also improved virus removal, but to a lesser extent. The experimental data indicates negatively charged MS2 viruses first adsorbed onto the positively charged iron oxyhydroxide floc particles before being removed by MF. MS2 viruses were not inactivated in iron or aluminum coagulation as evidenced by the fact that their concentrations before and after coagulation, settling, and re-suspension of the coagulated sludge were not statistically different.     

Peer reviewed: the promise of membrane technology

An expanded understanding of membrane technology is fostering new environmental applications.     

Mechanisms of virus control during iron electrocoagulation--microfiltration of surface water

Results from a laboratory-scale study evaluating virus control by a hybrid iron electrocoagulation - microfiltration process revealed only 1.0-1.5 log MS2 bacteriophage reduction even at relatively high iron dosages (∼13 mg/L as Fe) for natural surface water containing moderate natural organic matter (NOM) concentrations (4.5 mg/L dissolved organic carbon, DOC). In contrast, much greater reductions were measured (6.5-log at pH 6.4 and 4-log at pH 7.5) at similar iron dosages for synthetic water that was devoid of NOM. Quantitative agreement with Faraday’s law with 2-electron transfer and speciation with phenanthroline demonstrated electrochemical generation of soluble ferrous iron. Near quantitative extraction of viruses by dissolving flocs formed in synthetic water provided direct evidence of their removal by sorption and enmeshment onto iron hydroxide flocs. In contrast, only approximately 1% of the viruses were associated with the flocs formed in natural water consistent with the measured poor removals. 1-2 logs of virus inactivation were also observed in the electrochemical cell for synthetic water (no NOM) but not for surface water (4.5 mg/L DOC). Sweep flocculation was the dominant destabilization mechanism since the ζ potential did not reach zero even when 6-log virus reductions were achieved. Charge neutralization only played a secondary role since ζ potential → 0 with increasing iron electrocoagulant dosage. Importantly, virus removal from synthetic water decreased when Suwanee River Humic Acid was added. Therefore, NOM present in natural waters appears to reduce the effectiveness of iron electrocoagulation pretreatment to microfiltration for virus control by complexing ferrous ions. This inhibits (i) Fe²⁺ oxidation, precipitation, and virus destabilization and (ii) virus inactivation through reactive oxygen species intermediates or by direct interactions with Fe²⁺ ions.     

Disinfection by-product formation following chlorination of drinking water: Artificial neural network models and changes in speciation with treatment

Artificial neural network (ANN) models were developed to predict disinfection by-product (DBP) formation during municipal drinking water treatment using the Information Collection Rule Treatment Studies database complied by the United States Environmental Protection Agency. The formation of trihalomethanes (THMs), haloacetic acids (HAAs), and total organic halide (TOX) upon chlorination of untreated water, and after conventional treatment, granular activated carbon treatment, and nanofiltration were quantified using ANNs. Highly accurate predictions of DBP concentrations were possible using physically meaningful water quality parameters as ANN inputs including dissolved organic carbon (DOC) concentration, ultraviolet absorbance at 254 nm and one cm path length (UV₂₅₄), bromide ion concentration (Br⁻), chlorine dose, chlorination pH, contact time, and reaction temperature. This highlights the ability of ANNs to closely capture the highly complex and non-linear relationships underlying DBP formation. Accurate simulations suggest the potential use of ANNs for process control and optimization, comparison of treatment alternatives for DBP control prior to piloting, and even to reduce the number of experiments to evaluate water quality variations when operating conditions are changed. Changes in THM and HAA speciation and bromine substitution patterns following treatment are also discussed.     

Membrane rejection of nonspherical particles: Modeling and experiment

The rejection coefficient of nonspherical particles from ultrafiltration and microfiltration membranes has been examined from both theoretical and experimental perspectives. Modeling efforts focused on incorporating the convective hindrance factor for a capsule shaped particle in a cylindrical pore into predictions of the rejection coefficient. First, the convective hindrance factor was approximated using previously reported results for the hydrodynamic resistances experienced by a sphere in a pore. Second, computational fluid dynamics calculations predicted the convective hindrance factor for a capsule in a cylindrical pore. Results from both approaches indicate that including hydrodynamic interactions in predictions of the rejection coefficient has a greater effect for smaller particles and particles with smaller aspect ratio (i.e., close to spherical shape). Rejections of several rod‐shaped Gram negative bacteria with aspect ratio from 2 to 5 by clean track‐etched membranes were in general agreement with theoretical predictions. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3863–3873, 2013     

Physical–Chemical Treatment of Groundwater Contaminated by Leachate from Surface Disposal of Uranium Tailings

Leaching of trace elements including heavy metals, nonmetals, and radionuclides from surface impoundments of tailings generated during uranium mining and milling often leads to groundwater contamination. This paper reports results from coagulation and membrane filtration experiments designed to evaluate the capabilities of these processes to remove molybdenum, selenium, uranium, radium, thorium, and other mono- and divalent ions from contaminated groundwater in a shallow unconfined aquifer influenced by uranium tailings. A 10 mg Fe3+/L dose at pH 4 and 10 was found to be very effective for removing radium and thorium that were associated with particles in the raw water. Molybdenum and uranium removals by coagulation are consistent with surface complexation and electrostatic interactions between major coagulant and contaminant complexes in solution. Poor selenium removal suggests that selenate [Se(VI)] was the dominant species in the surficial groundwater. Permeation coefficients (intrinsic transport parameters) for dissolved ions and complexes across three new generation thin-film composite nanofiltration and reverse osmosis membranes evaluated obeyed Gaussian distributions with ionic charge having a mean value of zero. Thus, dissolved solute rejection from brackish multicomponent solutions appears to be only a function of the magnitude of ionic charge and not its sign (positive or negative). Solute permeation coefficients decreased in a power-law fashion with increasing product of molecular weight and absolute ion charge suggesting that both properties determine their removal by nanofiltration and reverse osmosis membranes. Because nanofiltration and reverse osmosis were found to be highly effective for removing a variety of ionic solutes they can be employed in pump and treat operations for groundwater purification prior to reinjection.     

Initial stages of bacterial fouling during dead-end microfiltration

Constant pressure experiments were performed using track-etched polycarbonate membranes and rod-shaped bacteria (viz., Brevundimonas diminuta and Serratia marcescens) to study flux decline and backwashing during the early stages of microfiltration. The intermediate blocking law originally derived for spherical particles was modified to account for the approximate cylindrical shape of the selected bacteria. A deposition factor was introduced to empirically account for the morphology of bacterial deposits. The initial stages of flux decline prior to the secretion of new extracellular polymeric substances (EPS) was quantitatively described by the intermediate blocking law before transitioning to cake filtration at later times. Scanning electron microscopy (SEM) provided additional visual evidence that bacteria simultaneously deposited directly on the membrane and on each other during early stages of filtration as assumed bythe intermediate blocking law. Empirical deposition factors decreased with initial permeate flux indicating its effect on bacteria deposition patterns, which was also confirmed by SEM. Bacteria were easily removed following short filtration times before significant secretion of new EPS by simply rinsing with ultrapure water, thereby completely restoring the clean membrane permeability. In contrast, this rinsing procedure did not completely recover the membrane permeability following longer durations when significant amounts of new EPS proteins and polysaccharides were secreted. Consequently, backwashing effectiveness during water and wastewater microfiltration will be high prior to EPS production whereas flux recovery may not be possible solely by hydrodynamic means once EPS are secreted.     

Temperature effects on the morphology of porous thin film composite nanofiltration membranes

Even though polymeric nanofiltration (NF) and reverse osmosis (RO) membranes often operate on surface waters and surficial groundwaters whose temperature varies over time and with season, very little detailed mechanistic information on temperature effects on membrane selectivity is available to date. Hence, a study was undertaken to investigate the effects of operating temperature (5-41 degrees C) on the morphology and structure of two commercially available thin film composite NF membranes. Application of hydrodynamic models to experimental rejection of dilute solutions of hydrophilic neutral alcohols, sugars, and poly(ethylene glycol)s revealed changes in both the sieving coefficient and permeability of solutes below the membrane glass transition temperature. The vast majority of pores were smaller than 2 nm for both membranes (network pores) even though evidence for a small fraction of larger aggregate pores (approximately 30 nm) was also obtained for one membrane. Increasing temperature appears to cause structural changes in network pores by increasing its pore size while simultaneously decreasing pore density. These increases in pore sizes partially explain reported reductions in contaminant (e.g. arsenic, salts, natural organic matter, hardness, etc.) removal by NF and RO membranes with increasing temperature.