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Utilities often test the effectiveness of different granular activated carbons (GACs) to determine which is most advantageous for their system. For surface water systems, in particular, the seasonal and annual variability of natural organic matter (NOM) in the source water makes it difficult to benchmark the effectiveness of GACs over multiple contract periods. This study produced stable, lyophilized NOM from the filtered water (FW), i.e., the influent to GAC contactors, which was then reconstituted (Recon) and tested against the FW itself in parallel rapid small-scale column tests (RSSCTs). The results demonstrated nearly identical NOM breakthrough profiles. RSSCTs conducted with both FW and Recon were shown to simulate the full-scale contactor performance well, while similar RSSCTs with regenerated GAC yielded a slightly earlier breakthrough, possibly due to the changes in GAC characteristics during regeneration and grinding. RSSCTs evaluating the removal of microcystin-LR (MC-LR) in the presence of background NOM contained in FW and Recon showed slightly different results, possibly due to the difference in chloride concentrations of these two waters. This work validates that reconstituted lyophilized NOM can be used as a source water surrogate for GAC evaluations when the constituent of interest is NOM, and potentially for other constituents depending upon the influence of additional inorganic constituents that were not evaluated as part of this study.

Per- and polyfluoroalkyl substances (PFAS) are increasingly of interest to drinking water utilities due to state regulations, the release of federal and state health advisories, and public concern. Pilot-scale data were fitted for 16 PFAS species and five commercial-activated carbons using an open-source pore and surface diffusion model that includes an automated parameter-fitting tool. The estimated model parameters are presented, and an uncertainty analysis was evaluated considering the expected temporal variability of influent concentrations. Expected treatment performance differed between two seasons in the pilot phase for the same carbon, which was not captured by modeled uncertainty. However, modeling results can support a utility's decision to choose activated carbon, and make design and operational decisions that can address changing water production rates and treatment goals. For the utility that undertook this pilot study and their desired treatment goals, granular activated carbon (GAC) was found to be an effective treatment technology for PFAS removal.

To assess the practical implications of various bottle materials used in anion exchange (IX) or granular activated carbon (GAC) isotherm experiments, adsorption of seven per- and polyfluoroalkyl substances (PFAS) onto three common bottle materials (silanized glass, polypropylene, and high-density polyethylene [HDPE]) were screened. Results were similar between bottle materials; therefore, only HDPE was used in a detailed bottle material isotherm study with 11 PFAS. For each PFAS, an HDPE bottle isotherm was generated with equilibrium liquid phase concentrations relevant to drinking water (

Sediment accumulation in drinking water storage facilities may lead to water quality degradation, including biological growth and disinfectant decay. The current research evaluated the microbiome present in a sediment after sequential exposure to monochloramine, free chlorine, and monochloramine. Chemical profiles within the sediment based on microelectrodes showed evidence of nitrification, and monochloramine slowly penetrated the sediment but was not measurable at lower depths. A metagenomic approach was used to characterize the microbial communities and functional potential of top (0–1 cm) and bottom (1–2 cm) layers in sediment cores. Differential abundance analysis revealed both an enrichment and depletion associated with depth of microbial populations. We assembled 30 metagenome-assembled genomes (MAGs) representing bacterial and archaeal microorganisms. Most metabolic functions were represented in both layers, suggesting the capability of the microbiomes to respond to environmental fluctuations. However, niche-specific abundance differences were identified in biotransformation processes (e.g., nitrogen). Metagenome-level analyses indicated that nitrification and denitrification can potentially occur simultaneously in the sediments, but the exact location of their occurrence within the sediment will depend on the localized physicochemical conditions. Even though monochloramine was maintained in the bulk water there was limited penetration into the sediment, and the microbial community remained functionally diverse and active.

Sediment accumulation in water storage tanks may protect microorganisms from disinfectant exposure, causing the degradation of water quality. However, microbial activity and disinfectant penetration within water storage sediment remain largely uncharacterized. This study evaluated the penetration of monochloramine and free chlorine into a 2 cm (20000 μm) deep drinking water storage tank sediment using microelectrodes. The sediment was successively exposed to monochloramine for 4 months, free chlorine for 2 months, and monochloramine for 2 months. Temporal monochloramine, free chlorine, dissolved oxygen (DO), pH, ammonium, nitrite, and nitrate profiles were acquired using microelectrodes. The results showed that complete monochloramine or free chlorine penetration was not observed. Likewise, DO never fully penetrated the sediment, progressing inward with time to a maximum depth of 10000 μm and indicating microbial activity persisted over the entire 8 months. Decreasing ammonium and increasing nitrate concentrations, with minimal nitrite accumulation, further demonstrated microbial activity and indicated complete sediment nitrification. There were measurable levels of ammonium, nitrite, and nitrate during free chlorine application, and nitrification activity gradually resumed upon a switch back to monochloramine. These findings suggest that the periodic removal of sediment from drinking water storage facilities is desirable to remove potentially protected environments for microorganisms.

Chloramine is a secondary disinfectant used to maintain microbial control throughout public water distribution systems. This study investigated the relationship between chloramine concentration, heterotrophic bacteria, and specific Mycobacterium species. Sixty-four water samples were collected at four locations within the utility's distribution network on four occasions. Water samples were analyzed for total chlorine and monochloramine. Traditional culture methods were applied for heterotrophic bacteria and nontuberculous mycobacteria (NTM), and specific quantitative polymerase chain reaction (qPCR) assays were used to detect and quantify Mycobacterium avium, M. intracellulare, and M. abscessus. Total chlorine and monochloramine concentrations decreased between the distribution entry point (4.7 mg/L and 3.4 mg/L as Cl2, respectively) to the maximum residence time location (1.7 mg/L and 1.1 mg/L as Cl2, respectively). Results showed that heterotrophic bacteria and NTM counts increased by two logs as the water reached the average residence time (ART) location. Microbiological detection frequencies among all samples were: 86% NTMs, 66% heterotrophic bacteria, 64% M. abscessus, 48% M. intracellulare, and 2% M. avium. This study shows that heterotrophic bacteria and NTM are weakly correlated with disinfectant residual concentration, R2=0.18 and R2=0.04, respectively. Considering that specific NTMs have significant human health effects, these data fill a critical knowledge gap regarding chloramine's impact on heterotrophic bacteria and Mycobacterial species survival within public drinking water distribution systems.

Per- and polyfluoroalkyl substances (PFAS) are receiving a great deal of attention from regulators, water utilities, and the general public. Anion-exchange resins have shown high capacities for removal of these substances from water, but there is currently a paucity of ion-exchange treatment models available to evaluate performance. In this work, important theoretical and practical considerations are discussed for modeling PFAS removal from drinking water using gel-type, strong-base anion-exchange resin in batch and column processes. Several important limitations found in the literature preclude movement toward model development, including the use of inappropriate isotherms, inappropriate kinetic assumptions, and experimental conditions that are not relevant to drinking water conditions. Theoretical considerations based on ion-exchange fundamentals are presented that will be of assistance to future researchers in developing models, designing batch and column experiments, and interpreting results of batch and column experiments.

Water-based opportunistic pathogens (OPs) are a leading cause of drinking-water-related disease outbreaks, especially in developed countries such as the United States (US). Physicochemical water quality parameters, especially disinfectant residuals, control the (re)growth, presence, colonization, and concentrations of OPs in drinking water distribution systems (DWDSs), while the relationship between OPs and those parameters remain unclear. This study aimed to quantify how physicochemical parameters, mainly monochloramine residual concentration, hydraulic residence time (HRT), and seasonality, affected the occurrence and concentrations of four common OPs (Legionella, Mycobacterium, Pseudomonas, and Vermamoeba vermiformis) in four full-scale DWDSs in the US. Legionella as a dominant OP occurred in 93.8% of the 64 sampling events and had a mean density of 4.27 × 105 genome copies per liter. Legionella positively correlated with Mycobacterium, Pseudomonas, and total bacteria. Multiple regression with data from the four DWDSs showed that Legionella had significant correlations with total chlorine residual level, free ammonia concentration, and trihalomethane concentration. Therefore, Legionella is a promising indicator of water-based OPs, reflecting microbial water quality in chloraminated DWDSs. The OP concentrations had strong seasonal variations and peaked in winter and/or spring possibly because of reduced water usage (i.e., increased water stagnation or HRT) during cold seasons. The OP concentrations generally increased with HRT presumably because of disinfectant residual decay, indicating the importance of well-maintaining disinfectant residuals in DWDSs for OP control. The concentrations of Mycobacterium, Pseudomonas, and V. vermiformis were significantly associated with total chlorine residual concentration, free ammonia concentration, and pH and trihalomethane concentration, respectively. Overall, this study demonstrates how the significant spatiotemporal variations of OP concentrations in chloraminated DWDSs correlated with critical physicochemical water quality parameters such as disinfectant residual levels. This work also indicates that Legionella is a promising indicator of OPs and microbial water quality in chloraminated DWDSs.

Natural organic matter (NOM) was collected, concentrated, and lyophilized on a monthly basis for 15 months to create a temporal NOM library and assess seasonal variability of untreated Ohio River water. Using fluorescence spectroscopy with parallel factor analysis, similar spectral components for both the ultrafiltered source water (UF1X) and reconstituted lyophilized NOM were observed in a two-component model throughout the study, with overall average emission and excitation wavelengths of 418 nm and 270 nm, respectively, for component 1 and 482 nm and 370 nm, respectively, for component 2. Fluorescence spectroscopy, high-pressure liquid chromatography-size exclusion chromatography, and elemental analysis indicated that the NOM was humic-like during the study with only small seasonal changes. Data from these analyses also demonstrated similarity between results for UF1X, reverse osmosis-concentrated NOM, and reconstituted- lyophilized NOM, validating the use of the reconstituted- lyophilized NOM as a surrogate for its source.

The effectiveness of granular activated carbon (GAC) for carcinogenic volatile organic compounds (cVOCs) has not been evaluated in the low- to sub- microgram per liter range. Rapid small scale column tests (RSSCTs) were employed to determine the GAC performance at empty bed contact times (EBCTs) of 7.5 and 15 minutes for 13 cVOCs at a target influent concentration of 5 μg/L in a typical groundwater matrix. Breakthrough was assessed for vinyl chloride, dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,2-dichloropropane, carbon tetrachloride, 1,3-butadiene, 1,1,1,2-tetrachloroethane, 1,2,3-trichloropropane, trichloroethylene and tetrachloroethylene. The throughput to breakthrough was found to be linearly correlated to capacities calculated with single-solute equilibrium isotherm parameters. Modest decreases, 9 to 13% on average, in throughput to 50% and 75% breakthrough were found when the EBCT was increased from 7.5 to 15 minutes. The carbon use rate (CUR), when scaled to simulate full-scale adsorption, indicated that GAC would be a viable technology for seven of the VOCs evaluated, with a CUR threshold less than 0.2 lbs/1000 gal. It may be possible to use 1,1 DCA and 1,2 DCA as surrogates for assessing chemicals near the feasibility limit.

Disinfectant biofilm penetration and its effect on biofilm aerobic activity and viability are still unclear. In this study, free chlorine and monochloramine were applied until full biofilm penetration occurred, and their effects on biofilm aerobic activity and viability were investigated in three dimensions throughout the entire biofilm depth, extending previous work where viability analysis was limited to the upper biofilm (50 μm depth), free chlorine penetration did not reach completion, and only one-dimensional (depth) profiles were obtained. The free chlorine and monochloramine biofilm concentration profiles were correlated spatially and temporally with aerobic microbial activity and cell-membrane integrity based viability using a combination of (1) microelectrode measurements for disinfectant penetration and (2) LIVE/DEAD BacLight staining, cryo-cross-sectioning, and confocal micrographs analysis for viability measurements throughout the entire biofilm depth. Compared to monochloramine, free chlorine penetration (1) was slower, (2) led to a greater decrease in biofilm thickness from sloughing, and (3) corresponded directly with a viability decrease. In addition, biofilm heterogeneity led to minor differences in either disinfectant's biofilm penetration, and prior biofilm exposure to monochloramine provided little impact to subsequent free chlorine biofilm penetration.

Natural organic matter (NOM) affects the stability and transport of nanoparticles (NPs) in natural waters by modifying their physiochemical properties. Source location, and seasonal variations, influence their molecular, physical and electrical charge properties. To understand the variations of NOM on the mobilization of NPs, large volumes of water were collected from the Ohio River (OR) over winter and summer seasons and dissolved NOMs were concentrated. The chemical and structural differences of these NOMs were compared with the Suwannee River humic acid (SRHA) SRHA using 1H and 13C nuclear magnetic resonance spectroscopy, and Fourier transforms infrared (FTIR) spectroscopy. Thermal analysis and FTIR confirmed that differences in composition, structure, and functional groups are a result of SRHA fractionation compared to whole molecule OR-NOM. The influence of OR-NOMs on the surface charge of CeO2 NPs and the effects on the transport and retention in a three-phase (deposition-rinse-re-entrainment) sand-packed columns were investigated at CeO2 NPs initial concertation of 10ppm, pH6.8, increasing ionic strength (3, 5, and 10mM), retention time of 1min, and increasing NOM concentration (1, 5, and 10ppm). The summer OR-NOM showed higher stabilization and mobilization effect on the CeO2 than the winter NOM; while their effect was very different form the SRHA. The stabilization of NPs is attributed to both electrostatic and steric effects. The differences in the chemical structure of the complex and heterogeneous NOMs showed disparate reactivity and direct impact on CeO2-NPs stability. Using SRHA to study the effect of NOM for drinking water related assessment does not sufficiently represent the natural conditions of the environment.

A method based on regression modeling was developed to discern the contribution of component chemicals to the toxicity of highly complex, environmentally realistic mixtures of disinfection byproducts (DBPs). Chemical disinfection of drinking water forms DBP mixtures. Because of concerns about possible reproductive and developmental toxicity, a whole mixture (WM) of DBPs produced by chlorination of a water concentrate was administered as drinking water to Sprague–Dawley (S–D) rats in a multigenerational study. Age of puberty acquisition, i.e., preputial separation (PPS) and vaginal opening (VO), was examined in male and female offspring, respectively. When compared to controls, a slight, but statistically significant delay in puberty acquisition was observed in females but not in males. WM-induced differences in the age at puberty acquisition were compared to those reported in S–D rats administered either a defined mixture (DM) of nine regulated DBPs or individual DBPs. Regression models were developed using individual animal data on age at PPS or VO from the DM study. Puberty acquisition data reported in the WM and individual DBP studies were then compared with the DM models. The delay in puberty acquisition observed in the WM-treated female rats could not be distinguished from delays predicted by the DM regression model, suggesting that the nine regulated DBPs in the DM might account for much of the delay observed in the WM. This method is applicable to mixtures of other types of chemicals and other endpoints.

Anaerobic treatment of domestic wastewater (DWW) produces dissolved methane that needs to be recovered for use as an energy product. Membrane-based recovery systems have been reported in the literature but are often limited by fouling. The objective of this study was to develop a methane producing biofilm on the shell side surface a membrane to allow for immediate recovery of methane as it was produced, negating mass transfer resistance caused by fouling. Between 89 and 96% of total methane produced was recovered via in-situ degassing without the need for fouling control or cleaning throughout 72 weeks of operation. High methane recovery efficiencies led to predictions of net positive energy yield in one reactor and a 32–61% reduction in energy demand in the others compared to the control. This research demonstrates the feasibility and usefulness of combining attached growth anaerobic wastewater treatment processes with hollow fiber membrane methane recovery systems for improved operation.

Per- and polyfluoroalkyl substances (PFAS) occurrence in drinking water and treatment methods for their removal are reviewed. PFAS are fluorinated substances whose unique properties make them effective surface-active agents with uses ranging from stain repellants to fire-fighting foams. In response to concerns about drinking water contamination and health risks from PFAS exposure, the United States Environmental Protection Agency published Health Advisories (HAs) for perfluorooctanoic acid and perfluorooctane sulfonic acid. The occurrence of six PFAS in drinking water has been reported in the Third Unregulated Contaminant Monitoring Rule (UCMR3), and subsequent analysis of the dataset suggested that four percent of water systems reported at least one detectable PFAS compound and 1.3 percent of water systems reported results above the HAs. Many treatment technologies have been evaluated in the literature, with the most promising and readily applied treatment technologies being activated carbon, anion exchange resins, and high-pressure membrane systems. From these data and literature reports, research and data gaps were identified and suggestions for future research are provided.

Many US water utilities using chloramine as their secondary disinfectant have experienced nitrification episodes that detrimentally impact water quality in their distribution systems. A semi-closed pipe-loop chloraminated drinking water distribution system (DWDS) simulator was used to evaluate the biological stability of the system and describe the response of microbial communities in the bulk water (BW) and biofilm (BF) phase to a disturbance caused by changes in the operational parameters. The DWDS simulator was operated through five successive operational schemes, including an episode of nitrification, followed by a ‘chlorine burn’ by switching the disinfectant from chloramine to free chlorine. Community comparisons showed significant differences in the structure based on disinfectant and phase (e.g., BW and BF). Both disturbances created changes in the relative abundances of the core microbiome and some members of the rare biosphere (i.e., conditionally rare taxa); however, the microbial community was resilient and returned to its stable state. Genes associated with multiple antibiotic resistance mechanisms were found to be a component of the core genomes of waterborne isolates. These results provide evidence of variations in the bulk water/biofilm microbial community structure during episodes of disturbance (e.g., disinfectant switching practices, nitrification) and its recovery after disturbance.

Monochloramine electrochemical determination in an aqueous system using newly fabricated gold and platinum microelectrodes was investigated to optimize sensor operation and to eliminate dissolved oxygen (DO) interference during monochloramine measurements. Carbon fiber microelectrodes were also compared for reference purposes. Gold and platinum microelectrodes exhibited no oxygen interference during monochloramine measurement and provided a linear relationship when operated at +150 and +300 mV vs. Ag/AgCl over a wide concentration range (0–4.2 mg Cl2/L), respectively. The carbon fiber microelectrode with 7-μm tip diameter was not sufficiently sensitive to monochloramine concentrations for detailed study. The baseline signal of both gold and platinum microelectrodes (i.e., signal without monochloramine) was near zero. With the same geometric tip diameter (20-μm tip diameter), gold microelectrodes resulted in better amperometric electrode response to monochloramine than platinum microelectrodes; gold microelectrodes had a higher sensitivity (52 ± 0.7 vs. 18 ± 0.07 pA/[mg Cl2/L]) and lower detection limit (0.12 ± 0.013 vs. 0.33 ± 0.10 mg Cl2/L), resulting in gold as the preferred microelectrode material. The developed gold microelectrode will allow accurate in situ monochloramine determination in biofilm while eliminating the confounding effects of oxygen interference.

Large volumes of water were collected from the Ohio River (OR) over winter and summer seasons to concentrate dissolved natural organic matter (NOMs) using reverse osmosis membranes and lyophilization. The chemical and structural differences were observed between both NOM samples and were compared to Suwannee River humic acid (SRHA) using (1)H and (13)C nuclear magnetic resonance spectroscopy, and Fourier transforms infrared spectroscopy. Thermal analysis was used to evaluate the macro-composition of samples. The influence of OR-NOMs on the surface charge of CeO(2) nanoparticles (NPs) and the effects on the transport and retention in sand-packed columns were investigated. The results indicated the properties of OR-NOM differ from SRHA. The summer OR-NOM showed a higher stabilizing and mobilizing of CeO(2), than the winter NOM. The stabilizing NPs is attributed to both electrostatic and steric effects. The differences in the chemical structure of the complex and heterogeneous NOMs showed disparate reactivity and effects with CeO(2)-NPs. The impact of OR-NOM on the fate and transport of NPs in drinking water treatment system could vary by the seasonal variation of source water NOM.

Annular reactors (ARs) were used to study biofilm community succession and provide ecological insight during nitrification arrestment through simultaneously increasing monochloramine (NH2Cl) and chlorine to nitrogen mass ratios, resulting in four operational periods (I-IV). Analysis of 16S rRNA-encoding gene sequence reads (454-pyrosequencing) examined viable and total biofilm communities and found total samples were representative of the underlying viable community. Bacterial community structure showed dynamic changes corresponding with AR operational parameters. Period I (complete nitrification and no NH2Cl residual) was dominated by Bradyrhizobium (total cumulative distribution: 38%), while environmental Legionella-like phylotypes peaked (19%) during Period II (complete nitrification and minimal NH2Cl residual). Nitrospira moscoviensis (nitrite-oxidizing bacteria) was detected in early periods (2%) but decreased to0.02% in later periods, corresponding to nitrite accumulation. Methylobacterium (19%) and members of Nitrosomonadaceae (42%) dominated Period III (complete ammonia and partial nitrite oxidation and low NH2Cl residual). An increase in Afipia (haloacetic acid-degrading bacteria) relative abundance (2% to 42%) occurred during Period IV (minimal nitrification and moderate to high NH2Cl residual). Microbial community and operational data provided no evidence of taxa-time relationship, but rapid community transitions indicated that the system had experienced ecological regime shifts to alternative stable states.

A highly selective needle type solid state amperometric nitrite microsensor based on direct nitrite oxidation on carbon fiber was developed using a simplified fabrication method. The microsensor's tip diameter was approximately 7 μm (14 μm spatial resolution). At an applied potential of +1.2 V vs. Ag/AgCl, the microsensor exhibited a linear nitrite response from 0 to 25 mg N L −1 , a 0.02 mg N L −1 (1.3 μM) limit of detection, and a fast response ( −1 nitrite per 1 pH unit change. Depending on the conditions (e.g., pH, alkalinity, nitrite concentration), pH may need to be taken into account during nitrite measurement. The developed carbon fiber nitrite microsensor successfully measured nitrite in a nitrifying biofilm and is applicable for in situ analysis in other micro-environments (e.g., microbial mats and sediments).

Biofilm communities in four bench-scale nitrifying biofilters degrading drinking water-regulated trihalomethanes were analyzed by next-generation high-throughput 454 pyrosequencing. On average, the bacterial communities were dominated by Nitrosomonas (69%), Nitrobacter (14%), and Chitinophagaceae (9%) with the dominant bacterial operational taxonomic unit (OTU) related to the ammonia-oxidizing bacteria (AOB) Nitrosomonas oligotropha. Even though ammonia-oxidizing archaea (AOA) have been reported in drinking water systems, the current study generated no PCR product or a very low yield of detectable Archaea amplicons, which may be attributed to biofilter operating conditions [e.g., 4 mg N/L TOTNH3 (sum of ammonia-nitrogen and ammonium-nitrogen)] that promoted AOB compared with AOA growth. Spatially within a given biofilter (influent to the effluent), OTU relative abundance significantly changed such that Nitrosomonas relative abundance decreased and Chitinophagaceae and Nitrobacter relative abundan...

A developmental toxicity bioassay was used in three experiments to evaluate water concentrates for suitability in multigenerational studies. First, chlorinated water was concentrated 135-fold by reverse osmosis; select lost disinfection by-products were spiked back. Concentrate was provided as drinking water to Sprague-Dawley and F344 rats from gestation day 6 to postnatal day 6. Maternal serum levels of luteinizing hormone on gestation day 10 were unaffected by treatment for both strains. Treated dams had increased water consumption, and increased incidences of polyuria, diarrhea, and (in Sprague-Dawley rats) red perinasal staining. Pup weights were reduced. An increased incidence of eye defects was seen in F344 litters. Chemical analysis of the concentrate revealed high sodium (6.6 g/l) and sulfate (10.4 g/l) levels. To confirm that these chemicals caused polyuria and osmotic diarrhea, respectively, Na₂SO₄ (5-20 g/l) or NaCl (16.5 g/l) was provided to rats in drinking water. Water consumption was increased at 5- and 10-g Na₂SO₄/l and with NaCl. Pup weights were reduced at 20-g Na₂SO₄/l. Dose-related incidences and severity of polyuria and diarrhea occurred in Na₂SO₄-treated rats; perinasal staining was seen at 20 g/l. NaCl caused polyuria and perinasal staining, but not diarrhea. Subsequently, water was concentrated ∼120-fold and sulfate levels were reduced by barium hydroxide before chlorination, yielding lower sodium (≤1.5 g/l) and sulfate (≤2.1 g/l) levels. Treatment resulted in increased water consumption, but pup weight and survival were unaffected. There were no treatment-related clinical findings, indicating that mixtures produced by the second method are suitable for multigenerational testing.

Drinking water treatment research can be complicated by difficulties in shipping large water quantities and changing natural organic matter (NOM) characteristics over time. To overcome these issues, it is advantageous to have a reliable method for concentrating NOM with minimal loss and maximum shelf-life. NOM concentration and preservation by lyophilization (freeze-drying) has been practiced for many years; however, little information for lyophilizing and reconstituting NOM exists in the literature. The purpose of this research was to both evaluate and improve the lyophilization process of a concentrated NOM solution and to determine the appropriate conditions (pH, mixing time, and concentration factor) under which to reconstitute lyophilized NOM for maximum total organic carbon (TOC) and ultraviolet absorbance at 254-nm (UV254 ) recovery. To achieve this, a new lyophilization method was developed, in which NOM concentrate is supercooled below its freezing point and heat transfer is carefully reg...

BaCO3 dispersed PVC composites were prepared through a polymer re-precipitation method. The composites were tested for sulfate removal using rapid small scale column test (RSSCT) and found to significantly reduce sulfate concentration. The method was extended to synthesize barium carbonate-loaded silica aero-gels-polyvinyl chloride (PVC) polymer composites. The PVC composites were characterized using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray mapping, X-ray diffraction (XRD), thermogravimetric analysis (TGA) and inductively coupled plasma mass spectrometry (ICP-MS) analysis. The method has advantages over conventional sulfate precipitation (sulfate removal process) using BaCO3 wherein clogging of the filter can be avoided. The method is environmentally friendly and does not interfere with natural organic matter as the conventional resin does. Some of the composites were thermally more stable as compared with the pure PVC discussed in the literature.

The U.S. Environmental Protection Agency's "Four Lab Study" involved participation of researchers from four national Laboratories and Centers of the Office of Research and Development along with collaborators from the water industry and academia. The study evaluated toxicological effects of complex disinfection byproduct (DBP) mixtures, with an emphasis on reproductive and developmental effects that have been associated with DBP exposures in some human epidemiologic studies. This paper describes a new procedure for producing chlorinated drinking water concentrate for animal toxicology experiments, comprehensive identification of100 DBPs, and quantification of 75 priority and regulated DBPs. In the research reported herein, complex mixtures of DBPs were produced by concentrating a natural source water with reverse osmosis membranes, followed by addition of bromide and treatment with chlorine. By concentrating natural organic matter in the source water first and disinfecting with chlorine afterward, DBPs (including volatiles and semivolatiles) were formed and maintained in a water matrix suitable for animal studies. DBP levels in the chlorinated concentrate compared well to those from EPA's Information Collection Rule (ICR) and a nationwide study of priority unregulated DBPs when normalized by total organic carbon (TOC). DBPs were relatively stable over the course of the animal studies (125 days) with multiple chlorination events (every 5-14 days), and a significant portion of total organic halogen was accounted for through a comprehensive identification approach. DBPs quantified included regulated DBPs, priority unregulated DBPs, and additional DBPs targeted by the ICR. Many DBPs are reported for the first time, including previously undetected and unreported haloacids and haloamides. The new concentration procedure not only produced a concentrated drinking water suitable for animal experiments, but also provided a greater TOC concentration factor (136×), enhancing the detection of trace DBPs that are often below detection using conventional approaches.

Chlorine microelectrodes with tip sizes of 5–15 μm were fabricated, fully characterized and evaluated under various environmental conditions, and used to measure high spatial resolution monochloramine profiles in biofilm. The chlorine microelectrode showed response to total chlorine, including free chlorine, monochloramine, and dichloramine under various conditions. Where monochloramine dominates the system at pH 8.0 and 4:1 Cl2:N, the chlorine microelectrode had sensitivity toward monochloramine concentrations (0.1–30.0 mg Cl2/L) at an applied potential of +550 mV (Ag/AgCl reference electrode) and 23 °C, and it was independent of pH ranges typical of drinking water (pH 6–9). Even though the electrode response shifted with DO changes, a linear relationship existed with monochloramine concentration for a given DO concentration. As a result, a 3D (response vs. DO vs. monochloramine concentration) calibration curve was required with DO present. Ultimately, this research will lead to the in situ application of chlorine microelectrodes for measurement of monochloramine within chloraminated drinking water system biofilm and, along with other microelectrodes (e.g. ammonia, pH, DO), will aid in elucidating nitrification phenomena occurring in the biofilm.

Monochloramine disinfection kinetics were determined for the pure-culture ammonia-oxidizing bacterium Nitrosomonas europaea (ATCC 19718) by two culture-independent methods, namely, Live/Dead BacLight (LD) and propidium monoazide quantitative PCR (PMA-qPCR). Both methods were first verified with mixtures of heat-killed (nonviable) and non-heat-killed (viable) cells before a series of batch disinfection experiments with stationary-phase cultures (batch grown for 7 days) at pH 8.0, 25°C, and 5, 10, and 20 mg Cl 2 /liter monochloramine. Two data sets were generated based on the viability method used, either (i) LD or (ii) PMA-qPCR. These two data sets were used to estimate kinetic parameters for the delayed Chick-Watson disinfection model through a Bayesian analysis implemented in WinBUGS. This analysis provided parameter estimates of 490 mg Cl 2 -min/liter for the lag coefficient ( b ) and 1.6 × 10 −3 to 4.0 × 10 −3 liter/mg Cl 2 -min for the Chick-Watson disinfection rate constant ( k ). While estimates of b were similar for both data sets, the LD data set resulted in a greater k estimate than that obtained with the PMA-qPCR data set, implying that the PMA-qPCR viability measure was more conservative than LD. For N. europaea , the lag phase was not previously reported for culture-independent methods and may have implications for nitrification in drinking water distribution systems. This is the first published application of a PMA-qPCR method for disinfection kinetic model parameter estimation as well as its application to N. europaea or monochloramine. Ultimately, this PMA-qPCR method will allow evaluation of monochloramine disinfection kinetics for mixed-culture bacteria in drinking water distribution systems.

Scale-up of a hollow-fiber-membrane (HFM) bioreactor treating trichloroethylene- (TCE-) contaminated water via co-metabolism with the methanotroph Methylosinus trichosporium OB3b PP358 was investigated through cost comparisons, bioreactor experiments, and mathematical modeling. Cost comparisons, based on a hypothetical treatment scenario of 568-L/min (150-gpm) flowrate with an influent TCE concentration of 100 microg/L, resulted in a configuration of treatment trains with two HFM modules in series and an overall annual cost of US dollar 0.36/m3 treated. Biological experiments were conducted with short lumen and shell residence times, 0.16 and 0.40 min, respectively, as a result of the cost comparisons. A new variable, specific transformation, was defined for characterizing the cometabolic transformation in continuous-flow systems, and values as large as 38.5 microg TCE/mg total suspended solids were sustainable for TCE treatment. Using mathematical modeling, HFM bioreactor system design was investigated, resulting in a five-step system design strategy to facilitate sizing of the unit processes.

Rodent toxicity studies typically use water bottles to administer test chemicals via drinking water. However, water bottles provide inconsistent exposure of volatile chemicals due to varying headspace, and lead to excessive waste of test material. To refine drinking water toxicity studies in rodents by enhancing sample quality and consistency, and minimizing waste, we designed and implemented a novel water delivery system that keeps the water chilled, headspace free and protected from light. Materials used were resistant to chemical interaction. In this gravity-fed system, a 6-L Teflon® water bag, stored in a polystyrene cooler on the cage rack, was connected to a stainless steel manifold delivering water to five cages via specialized drinking valves. Due to the absence of headspace in the water bag, this system allows consistent exposure of volatile chemicals. In addition, small diameter tubing throughout the system reduces the amount of test material residing in the system and minimizes chemical waste.

A hollow-fiber membrane bioreactor was used to separate trichloroethylene (TCE) from a gaseous waste stream with subsequent cometabolic biodegradation by a pure culture of Methylosinus trichosporium OB3b PP358. The two-stage bioreactor system was successfully operated for 20 days. PP358 was grown in a continuous-flow chemostat and circulated through the fiber lumen of a hollow-fiber membrane module (HFMM), while TCE contaminated air (141 to 191 microg/L) was pumped through the HFMM shell. Between 54% -84% TCE transfer and 92%-96% TCE cometabolism were obtained in the HFMM reactor loop. Short shell-residence times, 1.6 to 5.0 minutes, demonstrated quick throughput of TCE contaminated air. Best-fit computer modeling of the biological experiments estimated mass transfer coefficients between 2.0 x 10(-3) cm/min and 5.6 x 10(-3) cm/min. The average pseudo-first-order biodegradation rate constant for the biological experiments was 0.46 L/mg TSS/d. These results demonstrate that the hollow-fiber membrane bioreactor represents an attractive technology for the bioremediation of gaseous waste streams.

Rapid cometabolism of trichloroethylene (TCE) by pure cultures of Methylosinus trichosporium OB3b PP358 was demonstrated in a two-stage hollow-fiber membrane bioreactor over the course of 3 weeks. PP358 was grown in a continuous-flow chemostat and circulated through the shell of a hollow-fiber membrane module (HFMM), while TCE contaminated water was pumped through the fiber lumen. In parallel-flow HFMM biological experiments, 82% to 89% of the influent TCE was removed from the lumen with 99% of the transferred TCE undergoing biodegradation. Biological experiments in a larger capacity baffled radial-flow HFMM resulted in 66% to 99% TCE transferred and 93% to 96% TCE biodegradation at lumen residence times of between 1.5 and 3.7 min. Biodegradation was maintained throughout the experiments at pseudo-first-order biodegradation rate constants of 0.41 to 2.8 L/mg TSS/day. Best-fit computer modeling of the baffled radial-flow biological process estimated mass transfer coefficients as large as 2.7 {times} 10{sup {minus}2} cm/min. The computer model was also shown to simulate the experimental results quite well.

Drinking water distribution systems with ammonia present from either naturally occurring ammonia or ammonia addition during chloramination are at risk for nitrification. Nitrification in drinking water distribution systems is undesirable and may result in water quality degradation and subsequent noncompliance with existing regulations. Therefore, nitrification control is necessary to maintain water quality in drinking water systems when free ammonia is present. The fundamental processes affecting nitrification occurrence in distribution systems are discussed: (1) chloramine chemistry, (2) nitrifier growth kinetics, and (3) monochloramine inactivation kinetics along with a summary of nitrification monitoring and responses typically implemented at drinking water utilities.

Biodegradation of trichloroethlyene (TCE) in a hollow fiber membrane bioreactor was investigated using a mutant of the methanotrophic bacteria, Methylosinus trichosporium OB3b. Contaminated water flowed through the lumen (i.e., fiber interior), and the bacteria circulated through the shell side of the membrane module and an external growth reactor. In mass transfer studies with a radial cross-flow membrane module, 78.3-99.9% of the TCE was removed from the lumen at hydraulic residence times of 3-15 min in the lumen and the shell. In biodegradation experiments, 80-95% of the TCE was removed from the lumen at hydraulic residence times of 5-9 min in the lumen. The TCE transferred to the shell was rapidly biodegraded, with rate constants ranging from 0.16 to 0.9 L (mg of TSS) -1 day -1 . Radiochemical data showed that over 75% of the transferred TCE was biodegraded in the shell, with the byproducts being approximately equally divided between carbon dioxide and nonvolatiles. This study shows that a hollow fiber membrane bioreactor system coupled with the mutant strain PP358 of M. trichosporium OB3b is a very promising technology for chlorinated solvent biodegradation.

Drinking water treatment and disinfection byproduct (DBP) research can be complicated by natural organic matter (NOM) temporal variability. NOM preservation by lyophilization (freeze-drying) has been long practiced to address this issue; however, its applicability for drinking water research has been limited because the selected NOM sources are atypical of most drinking water sources. The purpose of this research was to demonstrate that reconstituted NOM from a lyophilized reverse-osmosis (RO) concentrate of a typical drinking water source closely represents DBP formation in the original NOM. A preliminary experiment assessed DBP formation kinetics and yields in concentrated NOM, which demonstrated that chlorine decays faster in concentrate, in some cases leading to altered DBP speciation. Potential changes in NOM reactivity caused by lyophilization were evaluated by chlorination of lyophilized and reconstituted NOM, its parent RO concentrate, and the source water. Bromide lost during RO concentration was replaced by adding potassium bromide prior to chlorination. Although total measured DBP formation tended to decrease slightly and unidentified halogenated organic formation tended to increase slightly as a result of RO concentration, the changes associated with lyophilization were minor. In lyophilized NOM reconstituted back to source water TOC levels and then chlorinated, the concentrations of 19 of 21 measured DBPs, constituting 96% of the total identified DBP mass, were statistically indistinguishable from those in the chlorinated source water. Furthermore, the concentrations of 16 of 21 DBPs in lyophilized NOM reconstituted back to the RO concentrate TOC levels, constituting 86% DBP mass, were statistically indistinguishable from those in the RO concentrate. This study suggests that lyophilization can be used to preserve concentrated NOM without substantially altering the precursors to DBP formation.

A developmental toxicity bioassay was used in three experiments to evaluate water concentrates for suitability in multigenerational studies. First, chlorinated water was concentrated 135-fold by reverse osmosis; select lost disinfection by-products were spiked back. Concentrate was provided as drinking water to Sprague-Dawley and F344 rats from gestation day 6 to postnatal day 6. Maternal serum levels of luteinizing hormone on gestation day 10 were unaffected by treatment for both strains. Treated dams had increased water consumption, and increased incidences of polyuria, diarrhea, and (in Sprague-Dawley rats) red perinasal staining. Pup weights were reduced. An increased incidence of eye defects was seen in F344 litters. Chemical analysis of the concentrate revealed high sodium (6.6 g/l) and sulfate (10.4 g/l) levels. To confirm that these chemicals caused polyuria and osmotic diarrhea, respectively, Na₂SO₄ (5-20 g/l) or NaCl (16.5 g/l) was provided to rats in drinking water. Water consumption was increased at 5- and 10-g Na₂SO₄/l and with NaCl. Pup weights were reduced at 20-g Na₂SO₄/l. Dose-related incidences and severity of polyuria and diarrhea occurred in Na₂SO₄-treated rats; perinasal staining was seen at 20 g/l. NaCl caused polyuria and perinasal staining, but not diarrhea. Subsequently, water was concentrated ∼120-fold and sulfate levels were reduced by barium hydroxide before chlorination, yielding lower sodium (≤1.5 g/l) and sulfate (≤2.1 g/l) levels. Treatment resulted in increased water consumption, but pup weight and survival were unaffected. There were no treatment-related clinical findings, indicating that mixtures produced by the second method are suitable for multigenerational testing.

Chloramine has replaced free chorine for secondary disinfection at many water utilities because of disinfection by-product (DBP) regulations. Because chloramination provides a source of ammonia, there is a potential for nitrification when using chloramines. Nitrification in drinking water distribution systems is undesirable and may result in degradation of water quality and subsequent non-compliance with existing regulations. Thus, nitrification control is a major issue and likely to become increasingly important as chloramine use increases. In this study, monochloramine penetration and its effect on nitrifying biofilm activity, viability, and recovery was investigated and evaluated using microelectrodes and confocal laser scanning microscopy (CLSM). Monochloramine was applied to nitrifying biofilm for 24 h at two different chlorine to nitrogen (Cl2:N) mass ratios (4:1 [4.4 mg Cl2/L] or 1:1 Cl2:N [5.3 mg Cl2/L]), resulting in either a low (0.23 mg N/L) or high (4.2 mg N/L) free ammonia concentration. Subsequently, these biofilm samples were allowed to recover without monochloramine and receiving 4.2 mg N/L free ammonia. Under both monochloramine application conditions, monochloramine fully penetrated into the nitrifying biofilm within 24 h. Despite this complete monochloramine penetration, complete viability loss did not occur, and both biofilm samples subsequently recovered aerobic activity when fed only free ammonia. When monochloramine was applied with a low free ammonia concentration, dissolved oxygen (DO) fully penetrated, but with a high free ammonia concentration, complete cessation of aerobic activity (i.e., oxygen utilization) did not occur and subsequent analysis indicated that oxygen consumption still remained near the substratum. During the ammonia only recovery phase, different spatial recoveries were seen in each of the samples, based on oxygen utilization. It appears that the presence of higher free ammonia concentration allowed a larger biomass to remain active during monochloramine application, particularly the organisms deeper within the biofilm, leading to faster recovery in oxygen utilization when monochloramine was removed. These results suggest that limiting the free ammonia concentration during monochloramine application will slow the onset of nitrification episodes by maintaining the biofilm biomass at a state of lower activity.

Biofilm in drinking water systems is undesirable. Free chlorine and monochloramine are commonly used as secondary drinking water disinfectants, but monochloramine is perceived to penetrate biofilm better than free chlorine. However, this hypothesis remains unconfirmed by direct biofilm monochloramine measurement. This study compared free chlorine and monochloramine biofilm penetration into an undefined mixed-culture nitrifying biofilm by use of microelectrodes and assessed the subsequent effect on biofilm activity and viability by use of dissolved oxygen (DO) microelectrodes and confocal laser scanning microscopy (CLSM) with LIVE/DEAD BacLight. For equivalent chlorine concentrations, monochloramine initially penetrated biofilm 170 times faster than free chlorine, and even after subsequent application to a monochloramine penetrated biofilm, free chlorine penetration was limited. DO profiles paralleled monochloramine profiles, providing evidence that either the biofilm was inactivated with monochloramine's penetration or its persistence reduced available substrate (free ammonia). While this research clearly demonstrated monochloramine's greater penetration, this penetration did not necessarily translate to immediate viability loss. Even though free chlorine's penetration was limited compared to that of monochloramine, it more effectively (on a cell membrane integrity basis) inactivated microorganisms near the biofilm surface. Limited free chlorine penetration has implications when converting to free chlorine in full-scale chloraminated systems in response to nitrification episodes.

Various medium compositions (phosphate, 1 to 50 mM; ionic strength, 2.8 to 150 meq/liter) significantly affected Nitrosomonas europaea monochloramine disinfection kinetics, as determined by the Live/Dead BacLight (LD) and propidium monoazide quantitative PCR (PMA-qPCR) methods (lag coefficient, 37 to 490 [LD] and 91 to 490 [PMA-qPCR] mg·min/liter; Chick-Watson rate constant, 4.0 × 10 −3 to 9.3 × 10 −3 [LD] and 1.6 × 10 −3 to 9.6 × 10 −3 [PMA-qPCR] liter/mg·min). Two competing effects may account for the variation in disinfection kinetic parameters: (i) increasing kinetics (disinfection rate constant [ k ] increased, lag coefficient [ b ] decreased) with increasing phosphate concentration and (ii) decreasing kinetics ( k decreased, b increased) with increasing ionic strength. The results support development of a standard medium for evaluating disinfection kinetics in drinking water.

Some epidemiological studies report associations between drinking water disinfection byproducts (DBPs) and adverse reproductive/developmental effects, e.g., low birth weight, spontaneous abortion, stillbirth, and birth defects. Using a multigenerational rat bioassay, we evaluated an environmentally relevant "whole" mixture of DBPs representative of chlorinated drinking water, including unidentified DBPs as well as realistic proportions of known DBPs at low-toxicity concentrations. Source water from a water utility was concentrated 136-fold, chlorinated, and provided as drinking water to Sprague-Dawley rats. Timed-pregnant females (P0 generation) were exposed during gestation and lactation. Weanlings (F1 generation) continued exposures and were bred to produce an F2 generation. Large sample sizes enhanced statistical power, particularly for pup weight and prenatal loss. No adverse effects were observed for pup weight, prenatal loss, pregnancy rate, gestation length, puberty onset in males, growth, estrous cycles, hormone levels, immunological end points, and most neurobehavioral end points. Significant, albeit slight, effects included delayed puberty for F1 females, reduced caput epidydimal sperm counts in F1 adult males, and increased incidences of thyroid follicular cell hypertrophy in adult females. These results highlight areas for future research, while the largely negative findings, particularly for pup weight and prenatal loss, are notable.