Effective enzyme activity: A proposed monitoring methodology for biofiltration systems with or without ozone.

"Effective Enzyme Activity", or simply "Effective Activity", is proposed as a biofiltration monitoring tool which combines enzyme activity with empty bed contact time (EBCT) to quantify biodegradation potential. The primary objective of this study was to evaluate the applicability of the Effective Activity concept for predicting water quality in biofiltration systems. This pilot-scale study evaluated eight different biofilter configurations in order to quantify impacts associated with filter media (anthracite/sand or granular activated carbon), pre-treatment (settled water with or without ozonation) and operating conditions (15- and 30-min EBCT, and backwash with or without chlorine). Microbial characterization included biomass concentration, as measured by adenosine triphosphate (ATP), in addition to esterase and phosphatase activity. Water quality parameters included dissolved organic carbon (DOC), trihalomethane (THM) formation potential (FP), haloacetic acid (HAA) FP, haloacetonitrile (HAN) FP, iodinated DBP FP (THMs and HAAs) and inorganic nutrients (phosphorus and nitrogen). Results confirmed the benefits to treated water quality associated with the application of an ozone residual of 0.5 mg/L, utilization of GAC filter media, eliminating chlorinated backwash, and extending EBCT. This study demonstrated a good relationship between effective esterase activity and reductions in DOC and THM FP, including those systems which incorporate pre-ozonation. As such, this study showed that Effective Activity may be appropriate for relating biomass characterization to treated water quality and highlights the importance of quantifying biomass activity in addition to quantity.

Impact of backwash on biofiltration-related nitrogenous disinfection by-product formation.

Previous studies have reported that biofilm extracted from full-scale biofilters can serve as nitrogenous disinfection by-product (N-DBP) precursors. Detached biofilm materials could escape during filter ripening and form N-DBP upon chloramination. This study examined the potential breakthrough of biofilm and N-DBP precursors during filter ripening at two water treatment plants (WTPs). The presence of biofilm material in aqueous samples was estimated by total adenosine triphosphate (tATP) levels; N-DBP formation potential (FP) tests were conducted under uniform formation conditions to quantify N-nitrosodimethylamine (NDMA) and haloacetonitrile (HAN4) precursors. While tATP peaks in filter effluent were observed post backwash at both WTPs, temporary increases of effluent NDMA FP were only observed during filter ripening where particle-associated NDMA precursors served as the dominant contributor. Overall, biofilters examined in this study demonstrated a consistent removal of NDMA FP regardless of the filter ripening process.

The contribution of biofilm to nitrogenous disinfection by-product formation in full-scale cyclically-operated drinking water biofilters.

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 ±â€¯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 ±â€¯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 ±â€¯0.27 ng NDMA/g media and 18.7 ±â€¯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 ±â€¯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 ±â€¯4.3 ng/L of NDMA precursors; typical NDMA UFC-FP of biofilter effluent was 8.5 ±â€¯2.6 ng/L.

Pilot-scale comparison of cyclically and continuously operated drinking water biofilters: Evaluation of biomass, biological activity and treated water quality.

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.

Removal of natural organic matter and disinfection byproduct precursors from drinking water using photocatalytically regenerable nanoscale adsorbents.

Disinfection byproduct precursors (DBPs) were removed from raw surface water obtained from two Canadian drinking water treatment plants via adsorption to two regenerable linear engineered TiO2 nanomaterials (LENs). The temperature employed in the final heating step of the LEN synthesis procedure was varied to produce two distinct nanomaterials, NB 550 and NB 700. The LENs had similar dimensions but differed in terms of surface characteristics, surface area, and crystal structure. Unlike the commercial TiO2 nanoparticles, both LENs were easily removed from the treated water via settling or filtration. Although neither of the LENs were as effective for NOM adsorption as commercial nanoparticles, both were able to remove substantial amounts of DBP precursors. NB 550 reduced the trihalomethane (THM) formation potential of both water sources by up to 40% and their haloacetic acid (HAA) formation potential by approximately 50%. NB 700 reduced the THM formation potential of one water source by 25% and that of the other by 40%. HAA precursor removal by NB 700 ranged from 25% to 30%. The adsorption of DOC, UV254, THM precursors, and HAA precursors by commercial nanoparticles and the LENs fit a modified Freundlich adsorption isotherm model. When the LENs were regenerated via exposure to UVA light they experienced a gradual loss in adsorption capacity of up to 50% over five regeneration cycles. This loss occurred more quickly for the less photoactive of the two nanomaterials, and was affected by water source, suggesting that components of the water matrices may have interfered with regeneration.

Modeling the exposure of wild fish to endocrine active chemicals: Potential linkages of total estrogenicity to field-observed intersex.

Decades of studies on endocrine disruption have suggested the need to manage the release of key estrogens from municipal wastewater treatment plants (WWTP). However, the proposed thresholds are below the detection limits of most routine chemical analysis, thereby restricting the ability of watershed managers to assess the environmental exposure appropriately. In this study, we demonstrated the utility of a mechanistic model to address the data gaps on estrogen exposure. Concentrations of the prominent estrogenic contaminants in wastewaters (estrone, estradiol, and ethinylestradiol) were simulated in the Grand River in southern Ontario (Canada) for nine years, including a period when major WWTP upgrades occurred. The predicted concentrations expressed as total estrogenicity (E2 equivalent concentrations) were contrasted to a key estrogenic response (i.e., intersex) in rainbow darter (Etheostoma caeruleum), a wild sentinel fish species. A predicted total estrogenicity in the river of ≥10 ng/L E2 equivalents was associated with high intersex incidence and severity, whereas concentrations <0.1 ng/L E2 equivalents were associated with minimal intersex expression. Exposure to a predicted river concentration of 0.4 ng/L E2 equivalents, the environmental quality standard (EQS) proposed by the European Union for estradiol, was associated with 34% (95% CI:30-38) intersex incidence and a very low severity score of 0.6 (95% CI:0.5-0.7). This exposure is not predicted to cause adverse effects in rainbow darter. The analyses completed in this study were only based on the predicted presence of three major estrogens (E1, E2, EE2), so caution must be exercised when interpreting the results. Nevertheless, this study illustrates the use of models for exposure assessment, especially when measured data are not available.

Multi-year prediction of estrogenicity in municipal wastewater effluents.

In this study, the estrogenicity of two major wastewater treatment plant (WWTP) effluents located in the central reaches of the Grand River watershed in southern Ontario was estimated using population demographics, excretion rates, and treatment plant-specific removals. Due to the lack of data on estrogen concentrations from direct measurements at WWTPs, the treatment efficiencies through the plants were estimated using the information obtained from an effects-directed analysis. The results show that this approach could effectively estimate the estrogenicity of WWTP effluents, both before and after major infrastructure upgrades were made at the Kitchener WWTP. The model was then applied to several possible future scenarios including population growth and river low flow conditions. The scenario analyses showed that post-upgrade operation of the Kitchener WWTP will not release highly estrogenic effluent under the 2041 projected population increase (36%) or summer low flows. Similarly, the Waterloo WWTP treatment operation is also expected to improve once the upgrades have been fully implemented and is expected to effectively treat estrogens even under extreme scenarios of population growth and river flows. The developed model may be employed to support decision making on wastewater management strategies designed for environmental protection, especially on reducing the endocrine effects in fish exposed to WWTP effluents.

Adsorption of natural organic matter and disinfection byproduct precursors from surface water onto TiO2 nanoparticles: pH effects, isotherm modelling and implications for using TiO2 for drinking water treatment.

Titanium dioxide is a photocatalyst that can remove organic contaminants of interest to the drinking water treatment industry, including natural organic matter (NOM) and disinfection byproduct (DBP) precursors. The photocatalytic reaction occurs in two steps: adsorption of the contaminant followed by degradation of the adsorbed contaminant upon irradiation with UV light. The second part of this process can lead to the formation of reactive intermediates and negative impacts on treated water quality, such as increased DBP formation potential (DBPfp). Adsorption alone does not result in the formation of reactive intermediates and thus may prove to be a safe way to incorporate TiO2 into drinking water treatment processes. The goal of this study was to expand on the current understanding of NOM adsorption on TiO2 and examine it in a drinking water context by observing NOM adsorption from real water sources and evaluating the effects of the resulting reductions on the DBPfp of the treated water. Bottle point isotherm tests were conducted with raw water from two Canadian water treatment plants adjusted to pH 4, pH 6 and pH 8 and dosed with TiO2 nanoparticles. The DOC results were a good fit to a modified Freundlich isotherm. DBP precursors and liquid chromatography with organic carbon detection NOM fractions associated with DBP formation were removed to some extent at all pHs, but most effectively at pH 4.

Comments on a Method to Measure Sucralose Using UV Photodegradation Followed by UV Spectrophotometry.

A simple and quick method to measure sucralose in aqueous solution at concentrations in the order of 0.1-1.2 g·L-1 proposed by Idris et al. uses UV irradiation prior to UV spectrophotometry. The photolysis of sucralose forms a photoactive compound characterized by maximum absorbance at approximately 270 nm. The conditions required for sucralose photolysis, however, had not been completely reported. In this work, the procedure described by Idris et al. was replicated using a low-pressure UV lamp to irradiate sucralose samples with a wider range of initial concentrations (0.04-10 g·L-1) with known fluences. It was determined that care must be taken to ensure that the same fluence is applied for both calibration and measurement steps because the absorbance of the sucralose photolysis product is a function of the applied fluence. The way the samples are irradiated also has an impact on the results in that the method exhibits a greater linear range if an apparatus is used that maximizes the fluence rate (e.g., by placing samples closer to the UV source or using a higher-intensity lamp).

Photocatalytic decomposition of selected estrogens and their estrogenic activity by UV-LED irradiated TiO2 immobilized on porous titanium sheets via thermal-chemical oxidation.

The removal of endocrine disrupting compounds (EDCs) remains a big challenge in water treatment. Risks associated with these compounds are not clearly defined and it is important that the water industry has additional options to increase the resiliency of water treatment systems. Titanium dioxide (TiO2) has potential applications for the removal of EDCs from water. TiO2 has been immobilized on supports using a variety of synthesis methods to increase its feasibility for water treatment. In this study, we immobilized TiO2 through the thermal-chemical oxidation of porous titania sheets. The efficiency of the material to degrade target EDCs under UV-LED irradiation was examined under a wide range of pH conditions. A yeast-estrogen screen assay was used to complement chemical analysis in assessing removal efficiency. All compounds but 17ß-estradiol were degraded and followed a pseudo first-order kinetics at all pH conditions tested, with pH 4 and pH 11 showing the most and the least efficient treatments respectively. In addition, the total estrogenic activity was substantially reduced even with the inefficient degradation of 17ß-estradiol. Additional studies will be required to optimize different treatment conditions, UV-LED configurations, and membrane fouling mitigation measures to make this technology a more viable option for water treatment.

Photocatalytic decomposition of organic micropollutants using immobilized TiO2 having different isoelectric points.

Organic micropollutants found in the environment are a diverse group of compounds that includes pharmaceuticals, personal care products, and endocrine disruptors. Their presence in the aquatic environment continues to be a concern as the risk they pose towards both the environment and human health is still inconclusive. Removal of these compounds from water and wastewater is difficult to achieve and often incomplete, but UV-TiO2 is a promising treatment approach. In this study, the efficiency of titanium dioxide (TiO2) immobilized on porous supports were tested for treatment of target pharmaceuticals and their metabolites under UV-LED exposure, a potential low energy and cost effective alternative to conventional UV lamps. Immobilization was completed using two different methods: (1) dip coating of TiO2 onto quartz fiber filters (QFT) or (2) thermal-chemical oxidation of porous titanium sheets (PTT). Comparison against experimental controls (dark QFT, dark PTT, and photolysis using UV-LED only) showed that UV-LED/PTT and UV-LED/QFT treatments have the potential to reduce the concentrations of the target compounds. However, the treatments were found to be selective, such that individual pharmaceuticals were removed well using QFT and PTT but not both. The complementary treatment behavior is likely driven by electrostatic interactions of charged compounds with the membranes. QFT membranes are negatively charged at the experimental pH (4.5-5) while PTT membranes are positively charged. As a result, cationic compounds interact more with QFT while anionic compounds with PTT. Neutral compounds, however, were found to be recalcitrant under any treatment conditions suggesting that ionic interactions were important for reactions to occur. This behavior can be advantageous if specificity is required. The behavior of pharmaceutical metabolites is similar to the parent compounds. However, isomeric metabolites of atorvastatin with functional groups in para and ortho configurations behave differently, suggesting that the positioning of functional groups can have an impact in their interaction with the immobilized TiO2. It was also apparent that PTT can be reused after cleaning by heat treatment. Overall, these newly synthesized membrane materials have potential applications for treatment of trace organic contaminants in water.

Fluorescence spectroscopy for monitoring reduction of natural organic matter and halogenated furanone precursors by biofiltration.

The application of fluorescence spectroscopy to monitor natural organic matter (NOM) reduction as a function of biofiltration performance was investigated. This study was conducted at pilot-scale where a conventional media filter was compared to six biofilters employing varying enhancement strategies. Overall reductions of NOM were identified by measuring dissolved organic carbon (DOC), and UV absorbance at 254 nm, as well as characterization of organic sub-fractions by liquid chromatography-organic carbon detection (LC-OCD) and parallel factors analysis (PARAFAC) of fluorescence excitation-emission matrices (FEEM). The biofilter using granular activated carbon media, with exhausted absorptive capacity, was found to provide the highest removal of all identified PARAFAC components. A microbial or processed humic-like component was found to be most amenable to biodegradation by biofilters and removal by conventional treatment. One refractory humic-like component, detectable only by FEEM-PARAFAC, was not well removed by biofiltration or conventional treatment. All biofilters removed protein-like material to a high degree relative to conventional treatment. The formation potential of two halogenated furanones, 3-chloro-4(dichloromethyl)-2(5H)-furanone (MX) and mucochloric acid (MCA), as well as overall treated water genotoxicity are also reported. Using the organic characterization results possible halogenated furanone and genotoxicity precursors are identified. Comparison of FEEM-PARAFAC and LC-OCD results revealed polysaccharides as potential MX/MCA precursors.

Rejection of pharmaceutically-based N-nitrosodimethylamine precursors using nanofiltration.

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 cutoff < 200 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.

Conventional drinking water treatment and direct biofiltration for the removal of pharmaceuticals and artificial sweeteners: A pilot-scale approach.

The presence of endocrine disrupting compounds (EDCs), pharmaceutically active compounds (PhACs) and artificial sweeteners are of concern to water providers because they may be incompletely removed by wastewater treatment processes and they pose an unknown risk to consumers due to long-term consumption of low concentrations of these compounds. This study utilized pilot-scale conventional and biological drinking water treatment processes to assess the removal of nine PhACs and EDCs, and two artificial sweeteners. Conventional treatment (coagulation, flocculation, settling, non-biological dual-media filtration) was compared to biofilters with or without the addition of in-line coagulant (0.2-0.8 mg Al(3+)/L; alum or PACl). A combination of biofiltration, with or without in-line alum, and conventional filtration was able to reduce 7 of the 9 PhACs and EDCs by more than 50% from river water while artificial sweeteners were inconsistently removed by conventional treatment or biofiltration. Increasing doses of PACl from 0 to 0.8 mg/L resulted in average removals of PhACs, EDCs increasing from 39 to 70% and artificial sweeteners removal increasing from ~15% to ~35% in lake water. These results suggest that a combination of biological, chemical and physical treatment can be applied to effectively reduce the concentration of EDCs, PhACs, and artificial sweeteners.

Engineered biofiltration for the removal of disinfection by-product precursors and genotoxicity.

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.

UV/chlorine control of drinking water taste and odour at pilot and full-scale.

Advanced oxidation processes (AOPs) can be used to destroy taste and odour-causing compounds in drinking water. This work investigated both pilot- and full-scale performance of the novel ultraviolet (UV)/chlorine AOP for the destruction of geosmin, 2-methylisoborneol (MIB) and caffeine (as a surrogate) in two different surface waters. The efficiency of the UV/chlorine process at pH 7.5 and 8.5 was comparable to that of the UV/hydrogen peroxide (UV/H2O2) process under parallel conditions, and was superior at pH 6.5. Caffeine was found to be a suitable surrogate for geosmin and MIB, and could be used as a more economical alternative to geosmin or MIB spiking for site-specific full-scale testing.

Formation of disinfection by-products in the ultraviolet/chlorine advanced oxidation process.

Disinfection by-product (DBP) formation may be a concern when applying ultraviolet light and free chlorine (UV/chlorine) as an advanced oxidation process (AOP) for drinking water treatment, due to typically large chlorine doses (e.g. 5-10 mg L(-1) as free chlorine). A potential mitigating factor is the low chlorine contact times for this AOP treatment (e.g. seconds). Full-scale and pilot-scale test results showed minimal trihalomethane (THM) and haloacetic acid (HAA) formation during UV/chlorine treatment, while dichloroacetonitrile (DCAN) and bromochloroacetonitrile (BCAN) were produced rapidly. Adsorbable organic halide (AOX) formation was significant when applying the UV/chlorine process in water that had not been previously chlorinated, while little additional formation was observed in prechlorinated water. Chlorine photolysis led to chlorate and bromate formation, equivalent to approximately 2-17% and 0.01-0.05% of the photolyzed chlorine, respectively. No perchlorate or chlorite formation was observed. During simulated secondary disinfection of AOP-treated water, DBP formation potential for THMs, HAAs, HANs, and AOX was observed to increase approximately to the same extent as was observed for pretreatment using the more common AOP of UV combined with hydrogen peroxide (UV/H2O2).

Effects of coagulation on the removal of natural organic matter, genotoxicity, and precursors to halogenated furanones.

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.

Factors affecting catalysis of copper corrosion products in NDMA formation from DMA in simulated premise plumbing.

This study investigated the effects of corrosion products of copper, a metal commonly employed in household plumbing systems, on N-nitrosodimethylamine (NDMA) formation from a known NDMA precursor, dimethylamine (DMA). Copper-catalyzed NDMA formation increased with increasing copper concentrations, DMA concentrations, alkalinity and hardness, but decreased with increasing natural organic matter (NOM) concentration. pH influenced the speciation of chloramine and the interactions of copper with DMA. The transformation of monochloramine (NH2Cl) to dichloramine and complexation of copper with DMA were involved in elevating the formation of NDMA by copper at pH 7.0. The inhibiting effect of NOM on copper catalysis was attributed to the rapid consumption of NH2Cl by NOM and/or the competitive complexation of NOM with copper to limit the formation of DMA-copper complexes. Hardness ions, as represented by Ca(2+), also competed with copper for binding sites on NOM, thereby weakening the inhibitory effect of NOM on NDMA formation. Common copper corrosion products also participated in these reactions but in different ways. Aqueous copper released from malachite [Cu2CO3(OH)2] was shown to promote NDMA formation while NDMA formation decreased in the presence of CuO, most likely due to the adsorption of DMA.

NDMA formation from amine-based pharmaceuticals--impact from prechlorination and water matrix.

The presence of N-nitrosodimethylamine (NDMA) in drinking water is most commonly associated with the chloramination of amine-based precursors. One option to control the NDMA formation is to remove the precursors via pre-oxidation, and prechlorination is among the most effective options in reducing NDMA formation. However, most of the findings to-date are based on single-precursor scenarios using the model precursor dimethylamine (DMA) and natural organic matter (NOM), while few studies have considered the potential interactions between water matrix components and the target precursors when investigating the prechlorination impact. Specifically, little is known for the behaviour of amine-based pharmaceuticals which have recently been reported to contribute to NDMA formation upon chloramination. This work demonstrates that prechlorination can affect both the ultimate NDMA conversion and the reaction kinetics from selected pharmaceuticals, and the nature and extent of the impact was compound-specific and matrix-specific. In the absence of NOM, the NDMA formation from most pharmaceuticals was reduced upon prechlorination, except for sumatriptan which showed a consistent increase in NDMA formation with increasing free chlorine contact time. In the presence of NOM, prechlorination was shown to enhance initial reactions by reducing the binding between NOM and pharmaceuticals, but prolonged prechlorination broke down NOM into smaller products which could then form new bonds with pharmaceuticals and thus inhibit their further conversion into NDMA.