Removal of 17β Estradiol and Fluoranthene by Nanofiltration and Ultrafiltration

With the recent emergence of endocrine disrupting compounds as an important potable drinking water and reclaimed wastewater quality issue, the removal of two estrogenic compounds (17β-estradiol and fluoranthene) by nanofiltration and ultrafiltration membranes was investigated. A less hydrophobic organic compound model species [parachlorobenzoic acid (PCBA)] was tested. 17β-estradiol (E2), fluoranthene, and PCBA were applied to the membrane in the presence and absence of natural organic matter (NOM). Both batch adsorption and dead-end stirred-cell filtration experiments indicated that adsorption is an important mechanism for transport/removal of relatively hydrophobic compounds, and is related to the octanol-water partition coefficient (KOW) values. All filtration measurements were performed approximately the same permeate flow rate in order to minimize artifacts from concentration polarization varied with different hydrodynamic operating conditions at the membrane interface. The percent removal by dead-end stirred-cell filtration ranged from 10 to >95% depending upon membrane pore size/hydrophobicity and presence/absence of NOM at an initial concentration ranging from 0.1 to 0.5 μM. Additional batch adsorption experiments with radio-label (3H) E2 at lower concentrations ranging 0.025 to 5 nM showed that E2 removal due to adsorption was independent of its initial concentration. Adsorption occurs both on the membrane surface and interior membrane pore surfaces. However, adsorption was insignificant for PCBA (log?KOW = 2.7), but removal presumably occurred due to electrostatic exclusion. Partition coefficients (log?K) of 0.44 to 4.86 measured in this study increased with log?KOW and membrane pore size.     

Estimation of Mass Transport Parameters of Organic Compounds through High Density Polyethylene Geomembranes Using a Modifield Double-Compartment Apparatus

A modified double-compartment apparatus (MDCA) is used to estimate mass transport parameters of organic compounds through high density polyethylene (HDPE) geomembranes and to investigate the effects of aging and external tension of HDPE geomembranes on the mass transport of organic compounds. A developed one-dimensional partition–diffusion mass transport model successfully explains the mass transport of the organic compounds through the HDPE geomembranes in a dilute aqueous solution–geomembrane system. Similar to batch immersion tests, the HDPE–water partition coefficient (KHDPE–W) values of organic compounds are found to have close relationships with the octanol–water partition coefficient and the aqueous solubility; furthermore, the diffusion coefficient (D) values decrease with the increase of their molecular diameter. For HDPE geomembranes served in the landfill liner for 5 years and stretched by 8% of their initial length, KHDPE–W values for organic compounds increase by 5–58%, D values for organic compounds increase by 10–86%, and breakthrough times are faster, indicating more amounts of organic compounds may break through the HDPE geomembrane in fields than expected. The mass transport parameters from MDCA tests could be used with those from batch immersion tests interchangeably after mass loss and immobilization of organic compounds in MDCA tests are considered.     

Permeation of BTEX through Unaged and Aged HDPE Geomembranes

The effects of aging of high-density polyethylene (HDPE) geomembranes on the diffusion and partitioning of a group of volatile organic compounds (VOCs) are examined. Two different 1.5?mm thick HDPE geomembranes were aged in the laboratory at 85°C by immersing in a synthetic leachate for up to 32?months. The results of partitioning and diffusion tests performed at room temperature on both unaged and aged geomembranes using a dilute aqueous solution containing four VOCs commonly found in landfill leachates [benzene, toluene, ethylbenzene, and xylenes (BTEX)] are reported. The diffusion and partitioning coefficients decreased with increased aging. The calculated permeation coefficients decreased by 36–62% after aging the geomembrane for about 10–32?months. This decrease in diffusion, partitioning, and permeation coefficients is related to the increase in geomembrane crystallinity during aging. A relationship between partitioning, diffusion, and permeation coefficients with the geomembrane crystallinity is established and could potentially be used to evaluate the migration of VOCs through HDPE geomembranes. Aging of HDPE geomembrane did not increase diffusive transport of organic contaminants.     

Effects of Bromide Ion and Natural Organic Matter Fractions on the Formation and Speciation of Chlorination By-Products

The impacts of bromide concentration and natural organic matter (NOM) characteristics on the formation and speciation of disinfection by-products (DBPs) in chlorinated NOM fractions were investigated. A total of 20 bulk water NOM fractions with a wide range of specific ultraviolet (UV) absorbance (SUVA254) values were obtained from a source water employing XAD-8 or XAD-4 resin adsorption in completely mixed batch reactors. SUVA was not a good predictor of DBP [trihalomethanes (THMs), haloacetic acids (HAAs), and adsorbable organic halogens (AOX)] formation and speciation. The destruction in the UV254 absorbance from chlorination did not correlate with DBP formation at any bromide level. NOM moieties which do not absorb UV light at 254?nm significantly contributed to DBP formation. Mass balance calculations on halogens using THMs, HAAs, and AOX data indicated that significant amounts of DBPs (>54% of AOX) other than THMs and HAAs were formed in NOM fractions with 60–110?μg/L bromide concentration. The relative occurrence of such other halogenated by-products decreased with increasing bromide concentrations up to 500?μg/L level. NOM in the studied water was more susceptible to the formation of brominated THM species as opposed to brominated HAAs. At constant dissolved organic carbon concentration, chlorine dose and pH, increasing bromide concentrations in NOM fractions increased the total concentrations of DBPs and resulted in a shift toward the formation of brominated species. Further, increasing bromide concentrations increased the spectrum of detected species (i.e., occurrence of all nine HAAs) and provided a competitive advantage to THM and HAA precursors in NOM over precursors of other DBPs.     

NOM Accumulation at NF Membrane Surface: Impact of Chemistry and Shear

The effects of solution chemistry, surface shear, and composition of natural organic matter (NOM) were investigated for their impact on accumulation of foulant material at the surface of charged polymeric nanofiltration membranes. The source of NOM was the Suwannee River. A bench-scale, batch recycle system was used with 20 hollow fiber, nanofiltration membranes. Membrane flux decline and foulant accumulation increased at low pH and high ionic strength as a result of neutralization of charge, electric double layer compression, and the apparent shift in conformation of charged NOM macromolecules. The rate of NOM accumulation decreased with operating time, suggestive of an eventual steady state between adsorption and desorption. The effect of NOM composition on membrane fouling could not be discerned by a standard technique to isolate hydrophobic and hydrophilic NOM fractions, quite possibly because of the fractionation methodology's failure to recover a small but important fouling fraction or because of NOM interactions that are lost when individual fractions are separately tested. However, a greater percentage of the hydrophilic than hydrophobic fraction permeated the membrane, in agreement with prior observations by others. Increasing the cross flow velocity from 85 to 255 cm∕s reduced the extent of flux decline, presumably due to hydrodynamic disruption of cake layer formation.     

Modeling the Transformation of Chromophoric Natural Organic Matter during UV/H2O2 Advanced Oxidation

This research developed a differential kinetic model to predict the partial degradation of natural organic matter (NOM) during ultraviolet plus hydrogen peroxide (UV/H2O2) advanced oxidation treatment. The absorbance of 254?nm UV, representing chromophoric NOM (CNOM) was used as a surrogate to track the degradation of NOM. To obtain reaction rate constants not available in the literature, i.e., reactions between the hydroxyl radical (?OH) and NOM, experiments were conducted with “synthetic” water, using isolated Suwannee River NOM, and parameter estimation was applied to obtain the unknown model parameters. The reaction rate constant for the reaction between ?OH and total organic carbon (TOC), k?OH,TOC, was estimated at 1.14(±0.10)×104??L?mg-1?s-1, and the reaction rate constant between ?OH and CNOM, k?OH,CNOM, was estimated at 3.04(±0.33)×104??L?mol-1?s-1. The model was evaluated on two natural waters to predict the degradation of CNOM and H2O2 during UV/H2O2 treatment. Model predictions of CNOM degradation agreed well with the experimental results for UV/H2O2 treatment of the natural waters, with errors up to 6%. For the natural water with additional alkalinity, the model also predicted well the slower degradation of CNOM during UV/H2O2 treatment, owing to scavenging of ?OH by carbonate species. The model, however, underpredicted the degradation of H2O2, suggesting that, when NOM is present, mechanisms besides the photolysis of H2O2 contribute appreciably to H2O2 degradation.     

Investigation of Consolidation-Induced Solute Transport. I: Effect of Consolidation on Transport Parameters

This paper presents an experimental investigation of the effect of clay consolidation on parameters that govern the advective-dispersive transport of an inorganic solute. Batch, diffusion, dispersion, and solute transport tests were conducted using kaolinite clay and dilute solutions of potassium bromide (KBr). Batch tests produced the highest levels of K+ sorption and indicated that equilibrium sorption was achieved in approximately 10–30 min. The increase in sorption observed in the batch tests, as compared to the dispersion or solute transport tests, reflects the significantly lower solids-to-solution ratio and more efficient mixing process. By comparison, kaolinite consolidation had little effect on sorption due to the relatively small change in porosity. Values of hydrodynamic dispersion coefficient (Dh), effective diffusion coefficient (D?), and apparent tortuosity factor decreased with decreasing porosity. Values of D? obtained for Br? were generally larger than for K+, whereas Dh values for Br? were significantly smaller than for K+. Values of longitudinal dispersivity (α) were larger for K+ than Br? and showed no clear trend with decreasing void ratio. In general, the experimental results suggest that changes in D? and Dh should be taken into account during clay consolidation whereas the sorption isotherm and α may be considered as unchanged during the consolidation process.     

Extradural temporopolar approach for giant pituitary adenomas invading the cavernous sinus and parasellar regions]

Natural organic matter (NOM) was extracted from a raw water source (Forge Pond, Granby, Mass.) and fractionated into eight groups: fulvic acid, humic acid, hydrophilic acid, weak hydrophobic acids, hydrophilic neutrals, hydrophobic neutrals, hydrophilic bases, and hydrophobic bases. The extent of adsorption of these fractions on preformed aluminum hydroxide flocs was determined. Also, the adsorption affinities of various fractions were correlated to selected NOM properties, i.e., organic charge, molecular weight, and specific ultraviolet absorbance. The nature of the reactions leading to adsorption was discussed, along with the induced dissolution of aluminum from the floc surface and its resulting association with NOM in particulate or colloidal forms.     

Mathematical modelling of drug transport in emulsion systems

Two mathematical models for the prediction of drug transport in triphasic (oil, water and micellar) emulsion systems as a function of micellar concentration have been developed and these models were evaluated by comparing experimental and simulated data. Fick's first law was used to derive a transport model for hydrophilic drugs, assuming that the oil/water (o/w) partitioning process was fast compared with membrane transport and therefore drug transport was limited by the membrane. Consecutive rate equations were used to model transport of hydrophobic drugs in emulsion systems assuming that the o/w interface acts as a barrier to drug transport. Benzoic acid and phenol were selected as hydrophilic model drugs. Phenylazoaniline and benzocaine were selected as hydrophobic model drugs. Transport studies at pH 3.0 and 7.0 were conducted using side-by-side diffusion cells. According to the hydrophilic model, an increase in micellar concentration is expected to decrease drug transport rates. The effective permeability coefficients (Peff) of drugs were calculated using an equation relating Peff and the total apparent volume of drug distribution (determined experimentally using drug/membrane permeability and partition coefficient values). The hydrophobic model was fitted to the experimental data for the cumulative amount of model drug in the receiver cells using a weighted least-squares estimation program (PCNONLIN). The oil/continuous phase partitioning rates (k1) and the membrane transport rates (k2) were estimated. The goodness of fit was assessed from the correlation coefficients of plots of predicted versus experimental data. The predicted data were consistent with the experimental data for both the hydrophilic and hydrophobic models.     

Volatile Organic Compound (VOC) Transport through Compacted Clay

Movement of volatile organic compounds (VOCs) through compacted clay liners was investigated using laboratory-scale column and tank tests. Hydraulic conductivity of the compacted clay was not significantly impacted by the introduction of VOCs in concentrations up to 20 mg∕L. Soil-water partition coefficients of the seven VOCs tested had a strong logarithmic relationship with the octanol-water partition coefficient. Partition coefficients from batch tests were in good agreement with those measured directly on soil samples at the termination of the column∕tank tests. The VOCs were degraded in the clay, with estimated half-lives ranging from 2 to 116 days. Mechanical dispersion was not significant in the range of the hydraulic conductivities of the test specimens (i.e., <10?7 cm∕s). Effective molecular diffusion coefficients were mostly in 10?6 cm2∕s and generally decreased with increasing aqueous solubility. Mass transport parameters of VOCs in clay liners can be estimated from laboratory batch tests and properly prepared small-scale column tests. However, accounting for degradation of VOCs and minimizing the number of transport parameters that are simultaneously estimated from a single response-time record are important considerations for accurate determination of transport parameters.     

Staged Coagulation for Treatment of Refractory Organics

Seasonal periods of high rainfall have been shown to cause elevated natural organic matter (NOM) loadings at treatment works. These high levels lead to difficulties in removing sufficient NOM to meet trihalomethane standards, and hence better alternative treatments are required. Here the removal of NOM was investigated by conventional coagulation treatment using both bulk and fractionated NOM. Initial experiments showed that over 70% removal of the hydrophobic and hydrophilic acid fractions was achieved at the works, while only 16% of the hydrophilic nonacid fraction was being removed. Bench scale jar testing of the isolated NOM fractions demonstrated that high removals of the hydrophobic fractions were achieved and that optimized conditions increased removal of the hydrophilic fractions, indicating that staged coagulation could be of benefit in the removal of the recalcitrant fractions. Experiments using optimized staged coagulation indicated that a small increase in the removal of the total NOM of this water was possible when compared to conventional treatment.     

Diffusive Transport of VOCs through LLDPE and Two Coextruded Geomembranes

The diffusive properties of two coextruded geomembranes, one with a polyamide inner core and the other with an ethylene vinyl-alcohol (EVOH) inner core, and a standard 0.53-mm (20-mil) linear low-density polyethylene (LLDPE) geomembrane were examined. Diffusion and sorption laboratory tests were performed to estimate the parameters controlling diffusive migration, including the partitioning, diffusion, and permeation coefficients of the geomembrane in both the aqueous and vapor phases. Results indicate a significant reduction in mass flux through the coextruded geomembranes compared to conventional LLDPE. The EVOH coextruded geomembrane had the lowest permeation coefficients (Pg) with a range of (2–6)×10?12?m2?s?1 for diffusion from the aqueous phase. These values for EVOH are upper bounds and the actual values may be lower than as stated. The polyamide (nylon) coextruded geomembrane had higher values than for EVOH, with a Pg range of (0.7–2.2)×10?11?m2?s?1 from the aqueous phase. The highest permeation coefficients were for the standard 20-mil LLDPE, which ranged from (0.6–1.1)×10?10?m2?s?1. Thus the permeation coefficient for LLDPE was about one order of magnitude greater than for the nylon coextruded and at least two orders of magnitudes higher than for the EVOH coextruded geomembrane. Both coextruded geomembranes showed decreased Pg values and therefore improved diffusive resistance to volatile organic compounds over traditional 0.56-mm PVC geomembranes. The EVOH geomembrane showed a 5–12-fold decrease in Pg in comparison to a 2.0-mm high density polyethylene geomembrane.     

Predicting Minimum Carbon Usage for PAC Adsorption of Trace Organic Contaminants from Natural Water

Powdered activated carbon (PAC) is an excellent adsorbent for drinking water treatment of many trace organic contaminants. To evaluate and design a PAC adsorption process for a particular application, it is necessary to know the minimum (lowest economical) carbon (adsorbent) usage (MCU) defined thermodynamically. In this work, an explicit relationship is developed for predicting the MCU required for a desirable level of treatment of a target trace organic compound (TC). The adsorption processes considered are PAC slurry contactors idealized either as batch reactors, plug flow reactors, or continuous-flow stirred tank reactors. Comparing with the ones previously available in the literature, this newly developed relationship, as a predictive tool for practical uses as well, is more accurate because it does not need to assume that the MCU required for target TC removal can always reduce the competing background natural organic matter (NOM) to a level much less than the NOM initial/influent concentration. Applications of the relationship developed herein to PAC adsorption of typical trace organic contaminants in natural water are demonstrated with isotherm data from multiple literature sources.     

Character of Organic Matter in Soil-Aquifer Treatment Systems

The objective of this study was to investigate the character and fate of bulk organics in reclaimed water used for groundwater recharge via soil-aquifer treatment (SAT). The study design followed a watershed guided approach considering hydraulically corresponding samples of drinking water sources, SAT-applied wastewater effluents, and subsequent post-SAT samples representing a series of different travel times in the subsurface. Water samples were fractionated into hydrophobic acids, transphilic acids, and hydrophilic carbon using a XAD resin-based protocol. Extensive characterization of organic carbon in the different samples was performed using state-of-the-art analytical techniques including excitation–emission matrix fluorescence spectroscopy, size exclusion chromatography, carbon-13 nuclear magnetic resonance spectroscopy (13C-NMR), Fourier transform infrared spectroscopy (FTIR), and elemental analysis. During SAT, transphilic and hydrophilic organic matter were preferentially removed. The results generally demonstrated that naturally derived (NOM) and effluent-derived organic matter after SAT overlap extensively in molecular weight distribution, amount and distribution of hydrophobic and hydrophilic carbon fractions, and chemical characteristics based on elemental analysis and 13C-NMR and FTIR spectroscopy. However, the residual portion of the dissolved organic carbon contained both effluent-derived organic matter and NOM.     

Iron Oxide Enhanced Chlorine Decay and Disinfection By-Product Formation

This study investigates the interaction of natural organic matter with iron oxide (goethite) on chlorine decay, disinfection by-product (DBP) formation, and DBP compound speciation [total trihalomethanes (TTHM4) and haloacetic acids (HAA5)]. Batch experiments were conducted with goethite, multiple finished drinking waters, variable chlorine dose, and fixed pH 8. The overall objective was to assess natural organic matter (NOM) adsorption onto goethite and its effect on chlorine decay and DBP formation. Chlorine consumption always increased in the presence of goethite and is attributed to an increase in the reactivity and/or modification of adsorbed NOM. Adsorbed NOM also led to an overall increase in TTHM4, however, HAA5 formation was suppressed during the first 2?h. Chloroform was identified as the increasing species and dichloracetic acid was identified as the suppressed species. This study clearly shows that goethite, which is the predominant iron oxide of pipe deposits, alters both chlorine decay and DBP formation and should be considered when assessing water treatment plant operations and DBP monitoring site selection.     

Use of Dubinin–Astakhov Equation to Describe Preloading Effect of Natural Organic Matter

This note presents a simple model to quantify the preloading effect of naturally occurring organic matter (NOM) in water on the adsorption capacity of activated carbon for a trace synthetic organic chemical (SOC). The model was developed from the Dubinin–Astakhov (DA) equation based on the assumption that the NOM preloading irreversibly reduced the limiting adsorption pore volume for the target SOC. Given that the DA-n value equal to one, the model reduces to a form similar to the one obtained by modifying the Freundlich equation directly. By assuming that the reduction of the limiting adsorption pore volume was proportional to the volume of NOM adsorbed, the NOM preloading effect was correlated directly to the amount of total organic carbon preloaded on the carbon. The resulting model was then compared with the experimental data in the literature. This simple model may be useful for certain practical applications that require only the estimation of the NOM preloading effect on the adsorption capacity of a target SOC from natural water.     

Effects of ultrafiltration on solute clearances in hollow fiber artificial kidneys

Although solute clearances in artificial kidney coils increase with ultrafiltration (UF), we have previously shown that increases are usually less than UF rate (most likely because of decreases in diffusive transport with UF coils and, for larger solutes, molecular sieving). The present studies demonstrate the effects of UF on clearances of Na and bromsulphalein (BSP) (mol. wt. 838) in hollow fiber dialyzers. Clearances were measured at increasing transmembrane hydrostatic pressures at perfusion rates of 200 and 500 ml. per minute. Fractions of total clearance attributable to diffusion as compared to solvent drag forces were calculated. Sieving coefficients were determined in studies where diffusion was minimized and clearance was primarily by solvent drag. Clearance increases were less than UF rate only for BSP; molecular sieving most likely accounts for the difference at high perfusion rates. Only at 200 ml. per minute was slight decrease of diffusion with UF suggested. Thus, in contrast to coils, there is minimal or no decrease in diffusion with UF in hollow fiber dialyzers.     

Impacts of Hydrophilic Membrane Additives on the Ultrafiltration of River Water

One of the most serious disadvantages of membrane applications in water treatment is the decreasing water permeation rate with time, which is often called fouling. This study investigates surface modification of polyethersulfone (PES) ultrafiltration membranes as a fouling reduction strategy for drinking water treatment applications. Surface modification was achieved through the addition of three different tailor-made hydrophilic surface modifying macromolecules (LSMM200, LSMM400, and LSMM600). Flat sheet membranes were prepared via a single-step casting procedure; their surface hydrophilicity was quantified via contact angle measurements. The incorporation of hydrophilic additives produced slightly more hydrophilic membranes (contact angle reduction of up to 8°) and improved membrane performance compared with the PES membrane without blending. In the treatment of highly colored river water, LSMM400- and LSMM600-modified membranes achieved up to 32% higher final fluxes. Surface modification resulted in significantly decreased flux reductions and natural organic matter accumulation. Dissolved organic carbon removals were approximately 70% for all the membranes studied. No clear correlation between membrane hydrophilicity and fouling reduction was observed.     

Diffusion of hydrogen in iron

A mass spectrometer was used to study hydrogen diffusion and trapping phenomena in fullyannealed and slightly cold-worked pure iron specimens which were in contact with distilled water or dilute acidic Buffer solutions. In the case of fully-annealed iron and slightly coldworked iron, hydrogen can diffuse into iron only when the iron contacts water directly. This diffusion phenomenon of hydrogen increased markedly with temperature and was accelerated by abrasion and hydrogen ion concentration in dilute acid. Abrasion and hydrogen ions in a dilute acidic Buffer solution did not affect the diffusion coefficient of hydrogen,D, but increased the hydrogen concentration at the iron surface contacting water or Buffer solution,C _s . The permeability of hydrogen in fully-annealed iron in contact with distilled water and the diffusion coefficient of hydrogen in fully-annealed and slightly cold-worked iron for the temperature range 10° to 100°C were measured. Trapping parameters in the slightly cold-worked iron were calculated.     

Oxygen transport through methacrylate-based hydrogels with potential biological capability

The permeability to oxygen of hydrogels prepared from copolymers of 2-hydroxymethyl methacrylate and p-methacryloxyl-oxyacetanilide have been studied by using an oxygen electrode in combination with a permeometer. The transmissibility Dk/L and the permeability Dk (where D, k and L are, respectively, the diffusion coefficient, the Henry constant and the thickness of the hydrogel) are measured by a combination of steady state and transitory state measurements. Both transport coefficients increase with the water content, which in turn depends on the copolymer composition. The values of these quantities tend toward a limiting value for water-saturated hydrogels. The ratio of the characteristic volume for diffusion of the oxygen molecule to the free volume of water per mole water is found to be in the vicinity of 0.10, and this value increases slightly as the fraction of the hydrophilic comonomer in the hydrogel increases. A detailed comparison of the biogels studied with six commercial contact lenses has also been performed.