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Incorporation of a carbon-based nutrient enhancement strategy for drinking water biofiltration is an attractive option, especially for source waters which contain recalcitrant organics. This study compared biofilters that were operated in parallel and individually enhanced with amino acids (including alanine, phenylalanine, and tryptophan), inulin, and sucrose to increase biomass concentration and promote biodegradation of dissolved organic carbon (DOC) in the source water, including disinfection by-product (DBP) precursors. Biomass activity was characterized by measuring adenosine tri-phosphate (ATP), dissolved oxygen (DO) consumption, and through the use of laccase and esterase enzyme assays. Performance was evaluated in terms of headloss, turbidity, pH, DOC, UV254, and DBP formation potential (DBP FP). The introduction of carbon-based nutrients significantly increased biomass activity, where ATP values peaked at 976 ng/g of filter media, 853 ng/g, and 513 ng/g for amino acids, inulin, and sucrose-spiked biofilters, respectively, while a non-spiked control only reached 104 ng/g. DO utilization by the enhanced biofilters was significantly higher than the control, with a strong correlation between ATP and DO uptake observed for all filters (R2 > 0.74). Laccase and esterase enzyme activities of enhanced biofilters were also elevated (p > 0.05), suggesting greater biodegradation potential. Operational parameters such as headloss development and turbidity control were not impaired by carbon supplementation strategies or an increase in biomass concentration and activity. However, the enhancement strategy did not provide improvement in terms of source water carbon removal (DOC and UV254) or DBP FP when treated filters were compared to a control.

Biofiltration has been shown to be effective for disinfection by-product (DBP) precursor control, however few studies have considered its role in the potential formation of DBPs. Biofilm is composed of heterogeneous bacteria as well as extracellular polymeric substances (EPS). The objective of this study was to determine the contribution of biofilm-related materials such as EPS to form nitrogen-containing DBPs upon chloramination, and to determine the influence of cyclical (scheduled on-off) biofilter operation on DBP precursor removal. Biologically active media was sampled from a full-scale biofilter operating under cold-water conditions (3.6 ± 0.5 °C) and extracted using a cation exchange resin into a phosphate buffer solution. Biomass concentrations, as determined using adenosine triphosphate (ATP) measurements, remained stable at 298 ± 55 ng ATP/g media over the trial period. N-nitrosodimethylamine (NDMA) and haloacetonitrile (HAN4) formation potential (FP) tests conducted under uniform formation conditions (UFC) using extracted biofilm yielded 0.80 ± 0.27 ng NDMA/g media and 18.7 ± 3.3 ng dichloroacetonitrile (DCAN)/g media. Further analyses of extracted biofilm using fluorescence spectroscopy and liquid chromatography-organic carbon detection indicated the presence of proteins above 20 kDa and humic-like substances. Extracted proteins (93.5 ± 8.1 μg/g media) correlated well (R = 0.90) with UV 280 measurements, indicating that spectrophotometry may serve as a valuable tool to quantify proteins in extracted biofilms. While substances in biofilms can serve as NDMA and DCAN precursors, the full-scale cyclically-operated biofilter that was examined did not show release of NDMA precursors during start-up following stagnation periods of 6 h or more. These biofilters consistently removed 6.9 ± 4.3 ng/L of NDMA precursors; typical NDMA UFC-FP of biofilter effluent was 8.5 ± 2.6 ng/L.

The objective of this pilot study was to evaluate the impact of cyclical (operated 8–12 h per day) and continuous biofilter operation with respect to biomass development, biological enzyme activity and treated water quality (in terms of organics, nutrients and disinfection by-product (DBP) formation potential). Continuously operated biofilters developed greater densities of biomass, as measured by ATP, when compared to cyclically operated filters; reducing the empty bed contact time (EBCT) increased biomass density under continuous flow conditions. However, once normalized to biomass, it was shown that cyclically operated filters exhibited higher enzyme activity, indicating that this method of operation may improve bacterial function. Reduction of organics was generally similar for both continuous and cyclical filters with the same EBCT, however, cyclical filters demonstrated higher variability during the first 4 h following start-up. Overall, HAA formation potential was better controlled by continuously operated filters, due to poor performance by the cyclical filters upon start-up while THM precursors were removed equally well by all filters. To understand the removal capacity for NDMA precursors through biological filters, both naturally occurring NDMA FP and NDMA FP resulting from spiked anthropogenic precursors was monitored through the filter depth. All the filters removed 90% of the naturally occurring NDMA FP within the first 45 cm; cyclical operation resulted in higher reduction of spiked anthropogenic NDMA precursors (50% higher than continuously operated) demonstrating the advantage of routine shut down on overall microbial activity. Tools to monitor and predict biofilter performance are in high demand. Here we present an “effective activity” term which combines enzyme activity with contact time (EBCT). Effective esterase activity was strongly correlated to DOC reduction as a function of filter operation (cyclical or continuous) and EBCT; effective phosphatase activity was indicative of phosphate removal. The results of this study indicate that routine shut down of the filters as this location improved enzyme activity without compromising control of chlorinated DBPs (THMs and HAAs) or NDMA derived from natural and anthropogenic precursors.

Many water providers monitor adenosine triphosphate (ATP) as an indicator of biological acclimation of their biofilters; however, strong correlations between ATP concentration and filter performance (e.g., organic matter or disinfection by-product precursor removal) are not typically observed. As an alternative, this study evaluated the use of enzyme activity for monitoring biological processes within filters. Recent studies have proposed that enzyme activity may be used as an indicator of biofilter function as it provides a means to quantify biodegradation which may allow for a more accurate measure of degradation potential and to gain a better understanding of biofilter performance. Sampling was completed from full- and pilot-scale biofilters to assess impacts associated with pre-treatments, varying sources waters, as well as pre-treatment and operating conditions. Enzyme activity (carboxylic esterase, phosphatase, s-glucosidase, α-glucosidase, s-xylosidase, chitinase, and cellulase) and ATP were measured from the top 5 cm of biofilter media representative of typical full-scale sampling; water quality parameters included dissolved organic carbon (DOC) and disinfection by-products (DBPs): trihalomethane (THM) formation potential (FP), and haloacetic acid FP (HAA FP). Results confirmed that ATP was not a reliable monitoring tool for DOC and DBP FP reduction in biofilters. A strong relationship was observed between esterase activity and DOC reduction; chitinase activity significantly correlated to THM FP reduction for filters treating three different source waters and HAA FP reduction achieved by filters treating the same source water with a range of pre-treatment and backwash conditions. This study showed that enzyme activity may be appropriate for monitoring biological processes within drinking water filters and may act as a surrogate for the removal of organic compounds.

The use of fluorescence data coupled with neural networks for improved predictability of drinking water disinfection by-products (DBPs) was investigated. Novel application of autoencoders to process high-dimensional fluorescence data was related to common dimensionality reduction techniques of parallel factors analysis (PARAFAC) and principal component analysis (PCA). The proposed method was assessed based on component interpretability as well as for prediction of organic matter reactivity to formation of DBPs. Optimal prediction accuracies on a validation dataset were observed with an autoencoder-neural network approach or by utilizing the full spectrum without pre-processing. Latent representation by an autoencoder appeared to mitigate overfitting when compared to other methods. Although DBP prediction error was minimized by other pre-processing techniques, PARAFAC yielded interpretable components which resemble fluorescence expected from individual organic fluorophores. Through analysis of the network weights, fluorescence regions associated with DBP formation can be identified, representing a potential method to distinguish reactivity between fluorophore groupings. However, distinct results due to the applied dimensionality reduction approaches were observed, dictating a need for considering the role of data pre-processing in the interpretability of the results. In comparison to common organic measures currently used for DBP formation prediction, fluorescence was shown to improve prediction accuracies, with improvements to DBP prediction best realized when appropriate pre-processing and regression techniques were applied. The results of this study show promise for the potential application of neural networks to best utilize fluorescence EEM data for prediction of organic matter reactivity.

A major drawback to ultrafiltration membrane operation for drinking water treatment is fouling, which results in lower water production and increased maintenance costs. The impact of different fouling mitigation strategies including, sparging conditions (duration and air flow rate) as well as phased in-line coagulation were investigated at pilot-scale. Unexpectedly, sparging during permeation and backwash resulted in a significantly higher rate of increase in irreversible resistance compared to Sparging only during backwash. Lower irreversible fouling observed without sparging during permeation was attributed to the formation of a protective layer on the membrane in the absence of sparging. Sparging at reduced air flow rates and intermittently, during the permeation cycle did not improve the irreversible resistance rate when compared to sparging only during backwash. The application of phased in-line coagulation to pre-coat membranes was also investigated. Coagulating for only the first half of the permeation cycle (phased coagulation) did not negatively impact membrane performance in terms of irreversible resistance and organics removal. Phased coagulation, which would lead to reduced coagulant and sludge disposal costs, appears to be a promising fouling control strategy.

Fluorescence spectroscopy as a means to detect low levels of treated wastewater impact on two source waters was investigated using effluents from five wastewater facilities. To identify how best to interpret the fluorescence excitation-emission matrices (EEMs) for detecting the presence of wastewater, several feature selection and classification methods were compared. An expert supervised regional integration approach was used based on previously identified features which distinguish biologically processed organic matter including protein-like fluorescence and the ratio of protein to humic-like fluorescence. Use of nicotinamide adenine dinucleotide-like (NADH) fluorescence was found to result in higher linear correlations for low levels of wastewater presence. Parallel factors analysis (PARAFAC) was also applied to contrast an unsupervised multiway approach to identify underlying fluorescing components. A humic-like component attributed to reduced semiquinone-like structures was found to best correlate with wastewater presence. These fluorescent features were used to classify, by volume, low (0.1-0.5%), medium (1-2%), and high (5-15%) levels by applying support vector machines (SVMs) and logistic regression. The ability of SVMs to utilize high-dimensional input data without prior feature selection was demonstrated through their performance when considering full unprocessed EEMs (66.7% accuracy). The observed high classification accuracies are encouraging when considering implementation of fluorescence spectroscopy as a water quality monitoring tool. Furthermore, the use of SVMs for classification of fluorescence data presents itself as a promising novel approach by directly utilizing the high-dimensional EEMs.

Certain unregulated disinfection byproducts (DBPs) are more of a health concern than regulated DBPs. Brominated species are typically more cytotoxic and genotoxic than their chlorinated analogs. The impact of granular activated carbon (GAC) on controlling the formation of regulated and selected unregulated DBPs following chlorine disinfection was evaluated. The predicted cyto- and genotoxicity of DBPs was calculated using published potencies based on the comet assay for Chinese hamster ovary cells (assesses the level of DNA strand breaks). Additionally, genotoxicity was measured using the SOS-Chromotest (detects DNA-damaging agents). The class sum concentrations of trihalomethanes, haloacetic acids, and unregulated DBPs, and the SOS genotoxicity followed the breakthrough of dissolved organic carbon (DOC), however the formation of brominated species did not. The bromide/DOC ratio was higher than the influent through much of the breakthrough curve (GAC does not remove bromide), which resulted in elevated brominated DBP concentrations in the effluent. Based on the potency of the haloacetonitriles and halonitromethanes, these nitrogen-containing DBPs were the driving agents of the predicted genotoxicity. GAC treatment of drinking or reclaimed waters with appreciable levels of bromide and dissolved organic nitrogen may not control the formation of unregulated DBPs with higher genotoxicity potencies. Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, Ministério da Educação//CAPES/Brasil Universidad de Costa Rica//UCR/Costa Rica University of Toronto//UofT/Canadá UCR::Vicerrectoría de Investigación::Unidades de Investigación::Ciencias Básicas::Centro en Investigación en Contaminación Ambiental (CICA)

N-Nitrosodimethylamine (NDMA) is a disinfection by-product (DBP) with many known precursors such as amine-containing pharmaceuticals that can enter the environment via treated wastewater. Reverse osmosis and tight nanofiltration membranes (MW cutoff200 Da) are treatment technologies that demonstrate high removal of many compounds, but at relatively high energy costs. Looser membranes (200 Da) may provide sufficient removal of a wide range of contaminants with lower energy costs. This study examined the rejection of pharmaceuticals that are known NDMA precursors (∼300 Da) using nanofiltration (MW cutoff ∼350 Da). MQ water was compared to two raw water sources, and results illustrated that NDMA precursors (as estimated by formation potential testing) were effectively rejected in all water matrices (84%). Mixtures of pharmaceuticals vs. single-spiked compounds were found to have no impact on rejection from the membranes used. The use of MQ water vs. surface waters illustrated that natural organic matter, colloids, and inorganic ions present did not significantly impact the rejection of the amine-containing pharmaceuticals. This study illustrates that NDMA formation potential testing can be effectively used for assessing NDMA precursor rejection from more complex samples with multiple and/or unknown NDMA precursors present, such as wastewater matrices.

Objectives Regular physical exercise may preserve β cell function in newly diagnosed adults with type 1 diabetes (T1D). However, clinical trials to test this theory require the recruitment and retention of adults with new-onset T1D, which can be challenging. We sought to determine the overall experiences of newly diagnosed adults with T1D in an exercise study, to understand issues that influence the retention of trial participants in such studies. Design Qualitative methodology using individual face-to-face (n=6) and telephone interviews (n=14). Interview transcripts were thematically analysed using the framework method. Setting The study took place at five participating UK hospitals. Participants Twenty participants, aged 19–55 years, in the Exercise for Type 1 Diabetes study were interviewed to explore their study experiences and identify motivators and deterrents towards the study. Participants in control and intervention arms were interviewed, as were people with T1D who had completed (n=16) and withdrawn (n=4). Results Participants revealed barriers and facilitators to retention; the majority were generalisable to clinical trials of people with newly diagnosed T1D. Coming to terms with a diagnosis of T1D, lack of time, work pressures, level of health professional support, volume, clarity and consistency of information and feedback and a desire for knowledge about their condition were all cited as influencing factors to trial retention. Conclusions To our knowledge, this is the first qualitative study to examine the experience of being involved in an exercise trial by people with T1D. Findings suggest appointments could be shorter, available outside of working hours and planned longer in advance; study information should be clear, consistent and in electronic and paper formats; questionnaires need minimising; healthcare support and feedback needs providing regularly; thought is required around how to support non-exercising arm participants. These considerations may improve participant retention rates in new-onset T1D studies.

Legacy lead and copper components are ubiquitous in plumbing of large buildings including schools that serve children most vulnerable to lead exposure. Lead and copper samples must be collected after varying stagnation times and interpreted in reference to different thresholds. A total of 130 outlets (fountains, bathroom and kitchen taps) were sampled for dissolved and particulate lead as well as copper. Sampling was conducted at 8 schools and 3 institutional (non-residential) buildings served by municipal water of varying corrosivity, with and without corrosion control (CC), and without a lead service line. Samples included first draw following overnight stagnation (8h), partial (30 s) and fully (5 min) flushed, and first draw after 30 min of stagnation. Total lead concentrations in first draw samples after overnight stagnation varied widely from 0.07 to 19.9 μg Pb/L (median: 1.7 μg Pb/L) for large buildings served with non-corrosive water. Higher concentrations were observed in schools with corrosive water without CC (0.9-201 μg Pb/L, median: 14.3 μg Pb/L), while levels in schools with CC ranged from 0.2 to 45.1 μg Pb/L (median: 2.1 μg Pb/L). Partial flushing (30 s) and full flushing (5 min) reduced concentrations by 88% and 92% respectively for corrosive waters without CC. Lead concentrations were10 μg Pb/L in all samples following 5 min of flushing. However, after only 30 min of stagnation, first draw concentrations increased back to45% than values in 1st draw samples collected after overnight stagnation. Concentrations of particulate Pb varied widely (≥0.02-846 μg Pb/L) and was found to be the cause of very high total Pb concentrations in the 2% of samples exceeding 50 μg Pb/L. Pb levels across outlets within the same building varied widely (up to 1000X) especially in corrosive water (0.85-851 μg Pb/L after 30MS) confirming the need to sample at each outlet to identify high risk taps. Based on the much higher concentrations observed in first draw samples, even after a short stagnation, the first 250mL should be discarded unless no sources of lead are present. Results question the cost-benefit of daily or weekly flushing as a remediation strategy. As such, current regulatory requirements may fail to protect children as they may not identify problematic taps and effective mitigation measures.

Disinfection by-products (DBPs) are formed when naturally occurring organic matter reacts with chlorine used in drinking water treatment, and DBPs formed in chlorinated drinking water samples have been shown to cause a genotoxic response. The objective of the current study was to further understand the principles of biofiltration and the resulting impacts on the formation of DBPs and genotoxicity. Pilot-scale systems were utilized to assess the performance of engineered biofilters enhanced with hydrogen peroxide, in-line coagulants, and nutrients when compared to passively operated biofilters and conventional treatment (coagulation, flocculation, sedimentation, non-biological filtration). Organic fractionation was completed using liquid chromatography-organic carbon detection (LC-OCD). Water samples were chlorinated after collection and examined for the removal of trihalomethane (THM), haloacetic acid (HAA), and adsorbable organic halide (AOX) precursors. Additionally, the formation potential of two halogenated furanones, 3-chloro-4(dichloromethyl)-2(5H)-furanone (MX) and mucochloric acid (MCA), and genotoxicity was determined. Biofiltration was shown to preferentially remove more DBP precursors than dissolved organic carbon (DOC). Formation potential of the unregulated DBPs, including MX and MCA, and genotoxic response was shown to be correlated to THM formation. These results infer that monitoring for THMs and HAAs provide insight to the formation of more mutagenic DBPs such as halogenated furanones, and that biofiltration may preferentially remove precursors to DBPs at a rate exceeding the removal of DOC.

Effective coagulation is essential to achieving drinking water treatment objectives when considering surface water. To minimize settled water turbidity, artificial neural networks (ANNs) have been adopted to predict optimum alum and carbon dioxide dosages at the Elgin Area Water Treatment Plant. ANNs were applied to predict both optimum carbon dioxide and alum dosages with correlation (R2) values of 0.68 and 0.90, respectively. ANNs were also used to developed surface response plots to ease optimum selection of dosage. Trained ANNs were used to predict turbidity outcomes for a range of alum and carbon dioxide dosages and these were compared to historical data. Point-wise confidence intervals were obtained based on error and squared error values during the training process. The probability of the true value falling within the predicted interval ranged from 0.25 to 0.81 and the average interval width ranged from 0.15 to 0.62 NTU. Training an ANN using the squared error produced a larger average interval width, but better probability of a true prediction interval.

Natural organic matter (NOM) in drinking water can react with disinfectants to form disinfection by-products (DBPs). Halogenated furanones are a group of emerging DBPs that can account for 20–60% of the total mutagenicity observed in drinking water. This study examined the impacts of bench-scale coagulation and subsequent chlorination on DBP formation as well as genotoxicity using three source waters located in Ontario, Canada. Two halogenated furanones 3-chloro-4-(dichloromethyl)-2(5H)-furanone (MX) and mucochloric acid (MCA) were analyzed; along with trihalomethanes (THMs), haloacetic acids (HAAs), and absorbable organic halides (AOX). NOM was quantified using liquid chromatography–organic carbon detection (LC–OCD). Measured MX and MCA formation was 6.9–15.3 ng/L and 43.2–315 ng/L following optimized coagulation and subsequent chlorination of the three waters tested. DBP formation and speciation were evaluated as a function of the specific NOM fractions present in the source waters. Humics, building blocks, and biopolymers were highly correlated with DBP formation. Correlations between DBPs were also investigated and a potential relationship between MCA and/or MX vs. HAAs was observed. MX was the only measured DBP that contributed to genotoxicity, representing less than 0.001% of AOX by mass but responsible for 40–67% of the genotoxic response in chlorinated Ottawa River water samples. Genotoxic potential decreased with alum dosages, signifying that coagulation was effective at removing genotoxic DBP precursors.

The potential application of fluorescence spectroscopy for monitoring of organic matter concentration and character at four water treatment facilities was investigated. Results are presented showing impacts on natural organic matter (NOM) due to intake location on the same water body and from individual unit processes including ozonation, granular-activated carbon filtration, and coagulation/flocculation. For validation and comparison of fluorescence methods, organic matter was quantified and characterized using liquid chromatography-organic carbon detection (LC-OCD). Principal component analysis (PCA) and parallel factors analysis were used for dimensionality reduction and to represent individual organic components observed through fluorescence excitation-emission matrices. Fluorescence results generally agreed with LC-OCD characterization, indicating that complete treatment reduced organic concentrations and preferential removal of humic-like material was associated with coagulation/flocculation. PCA results indicated higher concentrations of humic-like material at the Island water treatment plant intake that was not well reduced by inline polyaluminum chloride coagulation and direct filtration. Through fluorescence spectroscopy, ozonation increased Rayleigh scattering, which is correlated to small colloidal/particulate concentrations. Full-scale results from four water treatment plants presented demonstrate that fluorescence methods can characterize NOM, providing similar identification of trends to LC-OCD, with possible online application and use in real-time water treatment process control.

This work investigated the application of several fluorescence excitation–emission matrix analysis methods as natural organic matter (NOM) indicators for use in predicting the formation of trihalomethanes (THMs) and haloacetic acids (HAAs). Waters from four different sources (two rivers and two lakes) were subjected to jar testing followed by 24 hr disinfection by-product formation tests using chlorine. NOM was quantified using three common measures: dissolved organic carbon, ultraviolet absorbance at 254 nm, and specific ultraviolet absorbance as well as by principal component analysis, peak picking, and parallel factor analysis of fluorescence spectra. Based on multi-linear modeling of THMs and HAAs, principle component (PC) scores resulted in the lowest mean squared prediction error of cross-folded test sets (THMs: 43.7 (μg/L)2, HAAs: 233.3 (μg/L)2). Inclusion of principle components representative of protein-like material significantly decreased prediction error for both THMs and HAAs. Parallel factor analysis did not identify a protein-like component and resulted in prediction errors similar to traditional NOM surrogates as well as fluorescence peak picking. These results support the value of fluorescence excitation–emission matrix–principal component analysis as a suitable NOM indicator in predicting the formation of THMs and HAAs for the water sources studied.

A bench-scale study was performed to optimize backwash frequency and air sparging conditions during ultrafiltration (UF) for drinking water treatment in order to minimize hydraulically irreversible fouling as well as operating and maintenance costs. Surface shear stress representing different air sparging conditions (continuous coarse bubble, intermittent coarse bubble, and large pulse bubble) was applied in combination with various backwash frequencies (0.5, 2, and 6 hours) during UF of two natural surface waters. Results indicated that air sparging during permeation with intermittent coarse or large pulse bubbles significantly reduced the rate of irreversible fouling. This allowed for longer permeation times (up to 6 hours) between backwashing, when compared to a baseline condition which assumed a 0.5 h-backwash frequency with no air sparging during permeation. As a result, operation and maintenance cost savings estimated at > $350,000/year for a 29 MLD membrane train could be realized. This study demon...

A 14 month pilot-scale coagulation optimization study was conducted at the Peterborough Water Treatment Plant (Ontario, Canada) to compare treatment performance resulting from the application of aluminum sulfate vs. polyaluminum chloride (PACl). This paper describes results obtained from applying a statistical analysis approach to evaluate impacts on pH, turbidity, total organic carbon (TOC), ultraviolet absorbance (UVA), particle counts, chlorine residuals, filter head loss, flow rate, trihalomethanes (THMs), and nine haloacetic acids (HAA 9 ). To allow a direct comparison, parallel pilot trains were operated such that they achieved equal settled water TOC by adjusting PACl dose, (52–74% of the alum dose by weight). Settled water turbidity was significantly higher (on average 0.23 NTU) in the alum treated water when compared to PACl. For equivalent filter run-times, head loss was greater by 0.002–0.011 m h −1 when applying alum. An increase in pH by approximately 0.7 units when using PACl was observed to cause a significant increase in THM formation (10–30%).

This study investigated the impact of surface shear stress, to represent air sparging employed for fouling control, on the retention of organic micropollutants during ultrafiltration for drinking water treatment. The retention of 16 different pharmaceutically-active and endocrine disrupting compounds was examined during ultrafiltration of three natural surface waters (two lake, one river) under four different surface shear stress regimes: no shear stress, low peak shear stress (representative of continuous coarse bubble sparging), sustained peak shear stress (representative of intermittent coarse bubble sparging), and high peak shear stress (representative of large pulse bubble sparging). Results indicate that surface shear stress does impact the retention of emerging contaminants; however, it is dependent on water matrix and compound properties. The greatest retention of micropollutants was observed in waters with a higher concentrations of organic matter, and for conditions where no surface shear stress was applied (average 32% retention), and under conditions representative of large pulse bubble sparging (average 34% retention). The observed retention under conditions of no shear stress was likely due to a heavy fouling layer that altered the membrane selectivity and was able to entrap organic micropollutants of larger molecular weight. Under conditions that mimicked air sparging, increasing the shear stress (quantified as the root mean square applied shear) resulted in increased retention of organic micropollutants, particularly those that are neutral and hydrophobic in nature. This may be related to solute–solute complexes, which are kept in solution when shear stress is applied, or related to modification of the fouling layer by the shear stress induced onto the membrane surface. The results suggest that there may be value added with respect to removal of organic micropollutants, such as pharmaceuticals, when employing air sparging as a fouling control strategy during ultrafiltration.

Nanofiltration (NF) of seventeen pharmaceutically active (PhAC) and endocrine disrupting compounds (EDCs), representing a wide range of physicochemical properties, was investigated using both laboratory-prepared (Milli Q®) and natural waters. While previous studies have probed compound removal by membranes pre-fouled with model foulants, and the impact of natural water colloidal materials, this study examined the impact of compound interactions with key organic matter fraction(s), in the absence of colloidal and suspended particles. Lake Ontario water, a Great Lakes’ source of drinking water, was pre-treated using ultrafiltration to remove colloidal particles but retain organic matter. Additionally, the concentration of cations in the water matrix was varied. Experiments were conducted at a recovery (50%) comparable to a full-scale system. PhAC/EDC rejection from Milli Q® water increased as a function of molecular weight and molecular volume, but significantly decreased with increasing compound hydrophobicity. Dissolved organic matter (DOM) fractions were found to interact preferentially with neutral PhAC/EDCs, causing increased rejection, presumably due to enhanced size exclusion of compound-humic substance (HS) pseudo-complexes arising from dipole–dipole interactions. Increased cation concentration resulted in decreased removal of the neutral compounds; presumably due to reduced HS interaction sites. The rejection of specific ionic compounds was influenced by both size and charge effects of the compound-HS complexes.

The rejection of pharmaceutically active (PhACs) and endocrine disrupting compounds (EDCs) via a nanofiltration (NF) membrane was investigated as a function of naturally occurring colloidal and suspended particles, and cations. NF rejection of PhAC/EDCs was evaluated using a surface water that had been pre-treated by fluidized ion exchange (FIEX) to remove the humic fraction of dissolved organic matter yet retain the colloidal particles, and FIEX-pretreated water with cations added (Ca 2+ , Mg 2+ , Na + ). The presence of natural colloidal and suspended particles resulted in a significant decrease in the rejection of most neutral PhAC/EDCs, attributable to enhanced hydrophobic interactions (solute partitioning) at the membrane surface. The rejection of ionic compounds was governed by electrostatic interactions with the membrane surface and was not significantly affected by the presence of colloidal particles. The addition of cations to FIEX-pretreated water did not generally impact rejection of most compounds. While past research has investigated colloidal accumulation-associated NF/RO rejection of organic micropollutants, this study confirmed that colloidal particles indigenous to a typical surface water matrix negatively impact nanofiltration of PhAC/EDCs.

The effect of surface shear stress on membrane fouling during submerged hollow fiber ultrafiltration of three different surface waters (two lakes, one river) was investigated. Surface shear stresses that mimicked those induced when applying continuous and intermittent coarse bubble air sparging, large pulse bubble air sparging, as well as no air sparging were considered. The results suggest that fouling was mainly due to the accumulation of the biopolymer fraction of the natural organic matter present in the raw water. Inducing shear stresses onto the membrane surface significantly decreased the rate of membrane fouling (relative to no shear stress applied) in all waters tested. Of the shear stress conditions studied, that which mimicked large pulse bubble sparging had the greatest effect, reducing fouling by up to 80% when compared to conditions with no sparging applied. Conditions that mimicked intermittent and continuous coarse bubble fouling reduced the rate of fouling by up to 77 and 49%, respectively. These results suggest that the shear stresses induced by sparging can promote back transport of soluble organic material from the membrane surface. A semi-empirical relationship was developed to estimate the effect of raw water characteristics and applied sparging conditions on membrane fouling.

This study assessed the impact of chemical coagulation using alum on the removal of three endocrine-disrupting compounds (EDCs; bisphenol A, clofibric acid and estriol) and nine pharmaceutically active compounds (PhACs; acetaminophen, carbamazepine, diclofenac, gemfibrozil, ketoprofen, naproxen, pentoxifylline, sulfamethoxazole and sulfachloropyridazine). The impact on natural organic matter (NOM) fractions as determined using liquid chromatography–organic carbon detection (LC–OCD; total dissolved organic carbon (DOC), hydrophobic DOC, biopolymers, humic substances, building blocks, low molecular weight neutrals and acids) was also examined. Three test surface waters were included: Lake Ontario, Grand River and Otonabee River water (Ontario, Canada). Gemfibrozil concentrations were reduced in both Otonabee and Grand River waters. Reductions were noted for carbamazepine and (inconsistently) for acetaminophen, and estrone appeared to increase in concentration in Grand River water with increasing alum doses. NOM removal was primarily attributed to the humic fraction, with small reductions in biopolymers in all of the waters studied.

Halo-benzoquinones (HBQs) have been previously detected as disinfection by-products in chlorinated drinking water. The current work investigates the link between natural organic matter (NOM) characteristics and HBQ formation during bench-scale coagulation of raw water. Three source waters (Lake Ontario, Otonabee River and Grand River) were subjected to jar testing using alum followed by chlorination. NOM fractions were analyzed via liquid chromatography-organic carbon detection (LC-OCD), while HBQs were quantified using liquid chromatography-triple quadrupole mass spectrometry. One HBQ, 2,6-dichloro-(1,4)benzoquinone (2,6-DCBQ), was identified in all waters after chlorination, and appeared to decrease with increased applied alum dose. 2,6-DCBQ exhibited high correlations with some humic NOM indicators: humic substance concentration (in Grand and Otonabee River waters only), UV absorbance at 254 nm, UV absorbance at 254 nm of the humic peak, and specific UV absorbance of humics (humic SUVA). With data pooled from the three waters, the biopolymer fraction of NOM was most strongly correlated with 2,6-DCBQ formation (R(2) = 0.78, p < 0.001); this may be due to co-removal of biopolymers with HBQ precursors during coagulation. These results indicate that coagulation processes can be effective for reduction, but not elimination, of HBQ precursors.

Bench-scale tests were conducted to evaluate enhanced coagulation as a method for removing natural organic matter (NOM) from a surface water to reduce the formation of disinfection by-products (DBPs). Aluminium sulphate (alum) and two polyaluminium chloride (PACl) coagulants were used, as well as alum with pH depression. Using a PACl coagulant alone or alum with pH depression was shown to attain 35% removal of TOC at lower dosages (31 and 29 mg/L, respectively) when compared to the use of alum alone (43 mg/L). In addition to TOC and UV254, a fluorescence excitation–emission matrix (FEEM) approach and liquid chromatography–organic carbon detection (LC-OCD) were used to further characterize the removal of NOM in both untreated and filtered waters. Principal component analysis of FEEM was able to identify the presence of humic-like substances (HS), protein-like substances (PS), and colloidal/particulate matter (CPM); HS were found to have a close correlation with TOC and UV254. LC-OCD enabled the quantitative detection of hydrophobic and hydrophilic DOC; the latter was further separated into five components, the largest of which was HS. Strong linear correlations were calculated between TOC, UV254, HS, and hydrophilic DOC (r2 > 0.96); these parameters were also found to be closely correlated with the formation of trihalomethanes (THMs, r2 > 0.78) and haloacetic acids (HAAs, r2 > 0.92). Linear correlations with THMs and HAAs indicated that FEEM and LC-OCD provide good measures of DBP precursors when compared with TOC and UV254.

Filtration is the final physical barrier preventing the passage of microbial pathogens into public drinking water. Proper pre-treatment via coagulation is essential for maintaining good particle removal during filtration. To improve filter performance at the Elgin Area WTP, artificial neural network (ANN) models were applied to optimize pre-filtration processes in terms of settled water turbidity and alum dosage. ANNs were successfully developed to predict future settled water turbidity based on seasonal raw water variables and chemical dosages, with correlation (R2) values ranging from 0.63 to 0.79. Additionally, inverse-process ANNs were developed to predict the optimal alum dosage required to achieve desired settled water turbidity, with correlation (R2) values ranging from 0.78 to 0.89.

Granular media filtration is an important process in drinking water treatment to ensure the adequate removal of particle-bound pathogens (i.e., Giardia and Cryptosporidium). Filtration performance is typically monitored in terms of filtered water turbidity. However, particle counts may provide further insight into treatment efficiency, as they have a greater sensitivity for detecting small changes in filtration operation. Artificial neural networks (ANN) models were applied to optimize filtration at the Elgin Area water treatment plant (WTP) in terms of postfiltration particle counts. Process models were successfully developed to predict postfiltration particle counts. Two inverse-process models were developed to predict the optimal coagulant dosage required to attain target particle counts. Upon testing each model, a high correlation was observed between the actual and predicted data sets. The ANNs were then integrated into an optimization application to allow for the transfer of real-time data between t...

The detection of organic micropollutants, such as endocrine-disrupting compounds, pharmaceuticals and personal care products, in wastewater and the aquatic environment has brought increasing concern over their potential adverse ecological and human impacts. These compounds are generally present at trace levels (ng l −1 ) and in complex water matrices, such as wastewaters and surface waters, making their analysis difficult. Currently, no standardized analytical methods are available for the analysis of organic micropollutants in environmental waters. Owing to the diversity of physico-chemical properties exhibited by the various classes of organic micropollutants, the majority of established analytical methods described in the literature focus on a specific class of compounds, with few methods applicable to multi-class compound analysis. As such, analytical challenges and limitations contribute to the lack of understanding of the effectiveness of drinking water and wastewater treatment processes to remove organic micropollutants. This paper provides a practical overview of current analytical methods that have been developed for the analysis of multiple classes of organic micropollutants from various water matrices and describes the challenges and limitations associated with the development of these methods.

The impact of natural organic matter (NOM) and cations on the rejection of five endocrine disrupting compounds (EDCs) and pharmaceutically active compounds (PhACs) (acetaminophen, carbamazepine, estrone, gemfibrozil, oxybenzone) by nanofiltration (NF) was examined. The water matrices included membrane bioreactor (MBR) effluent, Lake Ontario water and laboratory-prepared waters modelled to represent the characteristics of the Lake Ontario water. The impact of cations in natural waters on compound rejection was also examined by doubling the natural cation concentration (calcium, magnesium, sodium) in both the Lake Ontario water and the MBR effluent. The presence of Suwannee River NOM spiked into laboratory-grade water was found to cause an increase in compound NF rejection. In addition, the presence of cations alone in laboratory-grade water did not have a significant impact on rejection with the exception of the polar compound gemfibrozil. However, when cation concentration in natural waters was increased, a significant decrease in the rejection of EDCs and PhACs was observed. This suggests that the presence of cations may result in a reduction in the association of EDCs and PhACs with NOM.

This study investigated the influence of water matrix characteristics, specifically natural organic matter (NOM) and divalent cations, on fouled nanofiltration (NF) membrane rejection by size exclusion. Membrane bioreactor effluent, Lake Ontario water and laboratory-prepared waters were filtered and the membrane effective molecular weight cut-off (MWCO) was measured. Analysis of the results for the laboratory-prepared waters showed that NOM caused a statistically significant reduction in effective MWCO (from 385 ± 13 Da to 343 ± 12 Da) whereas neither the influence of cations nor the interaction of NOM and cations was significant. The MWCO of the NF membrane was reduced from 385 ± 13 Da to 222 ± 46 Da and 348 ± 28 Da following filtration with the MBR effluent and Lake Ontario water, respectively. A previous study by the authors [A.M. Comerton, R.C. Andrews, D.M. Bagley, C. Hao, The rejection of endocrine disrupting and pharmaceutically active compounds by NF and RO membranes as a function of compound and water matrix properties, J. Membr. Sci., 313 (2008) 323] observed an increase in the rejection of endocrine disrupting compounds (EDCs) and pharmaceutically active compounds (PhACs) from MBR effluent and Lake Ontario water by the NF membrane when compared to laboratory-grade water. However, in this study the effective MWCO measured following filtration with Lake Ontario water was larger than the molecular weight of all 22 compounds (

This study examined the rejection of 22 endocrine disrupting compounds (EDCs) and pharmaceutically active compounds (PhAC) from raw and 5-μm filtered Lake Ontario water, membrane bioreactor effluent and laboratory-grade water (Milli-Q®) by ‘loose’ and ‘tight’ nanofiltration (NF) membranes and a reverse osmosis (RO) membrane. Rejection by the ‘tight’ NF membrane was most strongly correlated with compound log Kow and water solubility with the more hydrophobic compounds showing higher rejection. The RO membrane provided efficient EDC and PhAC removal (>90%). Conversely, in general, the ‘loose’ NF membrane offered poor and variable compound removal. Fouling and the presence of organic matter likely contributed to higher rejections of EDCs and PhACs while higher concentrations of divalent ions appeared to result in lower EDC and PhAC rejection by the membranes.

The overall objective of this study was to investigate the impact of blending membrane-treated water treatment plant (WTP) residuals with plant-filtered water on finished water quality in terms of biostability and disinfectant by-product (DBP) formation. Filter backwash water (FBWW) was treated with a pilot-scale ultrafiltration (UF) membrane to produce permeate that was blended with plant-finished water. The batch studies involved storing samples for a specified time with a disinfectant residual to simulate residence time in the distribution system. Both chlorinated and non-chlorinated FBWW streams were evaluated, and the experimental design incorporated free chlorine, monochloramine, and chlorine dioxide in parallel to a model system that did not receive a disinfectant dose. The results of the study found that blending 10% UF-treated FBWW with plant-filtered water did not have an impact on water biostability as monitored with heterotrophic plate counts (HPCs) or DBP concentrations as monitored by TTHM and HAA5 concentrations. However, the presence of preformed THM and HAA species found in chlorinated FBWW streams may result in higher levels of initial DBP concentrations in blended water matrices, and could have a significant impact on finished water quality in terms of meeting specific DBP guidelines or regulations.

Adsorption is one of the main mechanisms contributing to compound removal by membrane filtration, in addition to size exclusion and charge repulsion. In this study, the adsorption of 22 endocrine disrupting compounds and pharmaceutically active compounds by ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) membranes was investigated using 24-h bottle tests at 21 and 4 °C. Two natural waters (Lake Ontario and effluent from a membrane bioreactor (MBR)) and one laboratory-grade water were examined. Adsorption was strongly correlated with compound log Kow and membrane pure water permeability, and moderately correlated with compound water solubility. Adsorption was observed to be highest by the UF membrane followed by the NF and RO membranes. The influence of temperature on adsorption in the range examined was found to be insignificant. Three compounds for which deuterium-labelled surrogates were available (acetaminophen, carbamazepine, gemfibrozil) were examined to determine the influence of water matrix on adsorption. Adsorption of gemfibrozil may have been hindered due to competition for adsorption sites from the organic matter present in the lake water and MBR effluent.

Multiple conformations of a protein kinase target offer an opportunity to design small-molecule inhibitors with distinct but clinically useful profiles. This article analyzes and classifies the binding pockets in the kinase catalytic cleft in different conformational states. Targeting kinase multiple conformations as an emerging strategy in the field is exemplified with important small-molecule agents in the clinic. The structure-based analysis in the paper provides a rationale for thwarting the development of drug-resistant mutations in antikinase therapy.

This study evaluates the synergistic effects of ultraviolet (UV) and secondary disinfectants on water quality in a model distribution system. Chemical disinfectants evaluated for residual disinfection include chlorine dioxide, monochloramine, and free chlorine. Results suggest that there may be synergistic effects between UV and the chemical disinfectants for controlling microbiological re-growth in drinking water distribution systems. UV disinfection appeared to increase the vulnerability of bacteria located in suspension or within biofilms to chemical disinfection, although only at low disinfectant residual concentrations of 0.25, 0.50, and 1.0 mg/L for chlorine dioxide, free chlorine, and monochloramines, respectively. At high disinfectant residual concentrations of 0.50, 1.0, and 2.0 mg/L for chlorine dioxide, free chlorine, and monochloramines, respectively, results indicated that chemical disinfection alone would be adequate for microbial control. In the reactors receiving UV pre-treatment, both chlorine dioxide and free chlorine disinfection were far more effective in reducing the growth of suspended heterotrophic bacteria than without UV pre-treatment. Similar biofilm and suspended bacterial levels were observed without subsequent chemical disinfection regardless of the presence or absence of UV treatment. Overall, these findings imply that UV treatment prior to chemical disinfection enhances microbial control in distribution systems. These results indicate the use of UV pre-treatment can be effective at reducing the disinfectant concentration necessary for microbial control, therefore reducing the potential for the formation of disinfectant by-product in the system.Key words: drinking water, UV pre-treatment, chlorine dioxide, chlorine, monochloramines, disinfection.

Membrane bioreactors (MBRs) in combination with appropriate disinfection may provide sufficient wastewater treatment to produce effluent suitable for non-potable reuse. However, the ability of this technology combination to remove endocrine disrupting compounds (EDCs) has not been well studied. This study found that prior to disinfection a MBR removed greater than 96% of the influent cholesterol, coprostanol, and stigmastanol from municipal wastewaters compared to greater than 85% removal in a conventional treatment plant receiving the same influent. MBR effluent EDC concentrations were also lower for estrone, 17α-ethynylestradiol, and bisphenol A. Disinfection of MBR effluent with chlorine, chloramines, and chlorine dioxide provided no significant additional removal of estrone, 17β-estradiol, or 17α-ethynylestradiol but could remove 95% of added bisphenol A. Ultraviolet light at a dose appropriate for non-potable reuse did not affect removal of the target EDCs.Key words: endocrine disrupting compounds, membrane bioreactor, conventional treatment, disinfection.

Water quality parameters affecting sodium silicate performance in partial lead service line replacements were examined using a fractional factorial experimental design and static pipe systems. An external copper wire was used to create a galvanic connection between a former lead service line and a new copper pipe. The pipe systems were filled with lab prepared water made to mimic real water quality. Water was changed on a three times per week basis. A 2(4-1) fractional factorial design was used to evaluate the impact of alkalinity (15 mg L(-1) or 250 mg L(-1) as CaCO3), nitrate (1 mg L(-1) or 7 mg L(-1) as N), natural organic matter (1 mg L(-1) or 7 mg L(-1) as dissolved organic carbon), and disinfectant type (1 mg L(-1) chlorine or 3 mg L(-1) monochloramine), resulting in eight treatment conditions. Fractional factorial analysis revealed that alkalinity, natural organic matter and monochloramine had a significant positive effect on galvanic current. Natural organic matter and monochloramine also had a significant positive effect with respect to both total and dissolved lead release. For the treatment conditions examined, 67-98% of the lead released through galvanic currents was stored as corrosion scales and predominantly comprised of particulate lead (96.1-99.9%) for all eight treatments. The use of monochloramine and the presence of natural organic matter (7 mg L(-1)) were not favourable for corrosion control in sodium silicate-treated partial lead service line replacements, although further studies would be required to characterize optimal water quality parameters for specific water quality types. For utilities operating with sodium silicate as a corrosion inhibitor, this work offers further evidence regarding the consideration of chlorine as a secondary disinfectant instead of monochloramine, as well as the value of controlling natural organic matter in distributed water.