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This dissertation consists of five papers concerning nitrification in chloraminated drinking water distribution systems in a one and a half year field study. Seven finished waters were produced from different treatment processes and distributed to eighteen pilot distribution systems (PDSs) that were made pipes taken from actual distribution systems. Unlined cast iron (UCI), galvanized steel (G), lined cast iron (LCI), and PVC pipes were used to build the PDSs. All finished waters were stabilized and chloraminated before entering the PDSs. This dissertation consists of five major parts. (1) System variations of nitrates, nitrites, DO, pH, alkalinity, temperature, chloramine residuals and hydraulic residence times (HRT) during biological nitrification are interrelated and discussed relative to nitrification, which demonstrated Stoichiometric relationships associated with conventional biochemical nitrification reactions. Ammonia is always released when chloramines are used for residual maintenance in drinking water distribution systems, which practically insures the occurrence of biological nitrification to some degree. Biological nitrification was initiated by a loss of chloramine residual brought about by increasing temperatures at a five day HRT, which was accompanied by DO loss and slightly decreased pH. Ammonia increased due to chloramine decomposition and then decreased as nitrification began. Nitrites and nitrates increased initially with time after the chloramine residual was lost but decreased if denitrification began. Dissolved oxygen limited nitrifier growth and nitrification. No significant alkalinity variation was observed during nitrification. Residual and nitrites are key parameters for monitoring nitrification in drinking water distribution systems. (2) Using Monod kinetics, a steady state plug-flow kinetics model was developed to describe the variations of ammonia, nitrite and nitrate-N concentrations in a chloraminated distribution system. Active AOB and NOB biomass in the distribution system was determined using predictive equations within the model. The kinetic model used numerical analysis and was solved by C language to predict ammonia, nitrite, nitrate variation. (3) Nitrification control strategies were investigated during an unexpected episode and controlled study in a field study. Once nitrification began, increasing chloramine dose from 4.0 to 4.5 mg/L as Cl2 and Cl2:N ratio from 4/1 to 5/1 did not stop nitrification. Nitrification was significantly reduced but not stopped, when the distribution system hydraulic retention time was decreased from 5 to 2 days. A free chlorine burn for one week at 5 mg/L Cl2 stopped nitrification. In a controlled nitrification study, nitrification increased with increasing free ammonia and Cl2:N ratios less than 5. Flushing with increased chloramine concentration reduced nitrification, but varying flush frequency from 1 to 2 weeks had no effect on nitrification. (4) HPC variations in a chloraminated drinking water distribution system were investigated. Results showed average residual and temperature were the only water quality variables shown to affect HPC change at a five day distribution system hydraulic residence time was five days. Once nitrification began, HPC change was correlated to HRT, average residual and generated nitrite-N in the distribution system. (5) Biostability was assessed for water treatment processes and distribution system pipe by AOCs, BDOCs, and HPCs of the bulk water, and by PEPAs of the attached biofilms. All membrane finished waters were more likely to be biologically stable as indicated by lower AOCs. RO produced the lowest AOC. The order of biofilm growth by pipe material was UCI > G > LCI > PVC. Biostability decreased as temperature increased.

Total lead release in drinking water in the presence of free chlorine and chloramine residuals was investigated in field, laboratory and fundamental investigations for finished waters produced from ground (GW), surface (SW), saline (RO) and blended (B) sources. Field investigations found more total lead was released in the presence of chloramines than in the presence of free chlorine for RO and blended finished waters; however, there were no statistical differences in total lead release to finished GW and SW. Laboratory measurements of finished waters oxidation-reduction potential (ORP) were equivalent by source and were not affected by the addition of more than 100 mg/L of sulfates or chlorides, but were significantly higher in the presence of free chlorine relative to chloramines. Development of Pourbaix diagrams revealed the PbO2 was the controlling solid phase at the higher ORP in the presence of free chlorine and Pb3(CO3)2(OH)2(s) (hydrocerussite) was the controlling solid phase in the presence of chloramines at the lower ORP, which mechanistically accounted for the observed release of total lead as PbO2 is much less soluble than hydrocerussite. The lack of differences in total lead release to finished GW and SW was attributed to differences in water quality and intermittent behavior of particulate release from controlling solid films.

Corrosion of distribution system piping and home plumbing materials is a major concern in the water community. Iron release adverse affects aesthetic water quality and the release of copper and lead is regulated by the Lead and Copper rule (LCR) and can adversely affect consumer health. Corrosion control is typically done by pH regulation and/or addition of corrosion inhibitors. Monitoring of corrosion control is typically done after the fact by monitoring metal release, functional group concentration of the selected chemical species or water quality. Hence, the associated laboratory analyses create a significant delay prior to the assessment of corrosion in drinking water systems. As corrosion in drinking water systems is fundamentally an electrochemical process, measurement of the electrical phenomena associated with corrosion can be use for real-time corrosion monitoring. This dissertation focuses on using parameters associated with electrochemical corrosion monitoring (EN) measurements in a field facility to predict and control the release of Iron, Copper and Lead in finished waters produced from ground, surface and saline sources with and without usage of corrosion inhibitors. EN data has not been used previously to correlate water quality and metal release; hence the use of EN data for corrosion control in drinking water systems has not been developed or demonstrated. Data was collected over a one year period from a large field facility using finished waters that are distributed to each of the fourteen pilot distribution systems (PDSs), corrosion loops and Nadles each. The PDSs have been built from aged pipes taken from existing distribution systems and contain links of PVC, lined cast Iron, unlined cast Iron and galvanized Steel pipe. The effluent for each PDS was split in two parts. One was delivered to the corrosion loops which are made from coiled copper pipe with lead-tin coupon inserted inside each loop and the other was delivered to the Nadles which housed the EN probes with electrodes for Fe or Cu or Pb-Sn. Finished water quality was monitored in and out of each PDS and total and dissolved Copper and Lead were monitored out of each corrosion loop. Photographs, scanning electron microscope (SEM) micrographs and energy disruptive x-ray spectroscopy (EDAX) conducted on all EN electrodes. EN electrodes showed dark brown to blackish voluminous scales for Fe, and EDAX revealed occurrence of two scales in distinct areas for all Fe electrodes; one comprised of porous, spongy looking structures and scales with more Fe content where the other had denser and more compact scales richer in Ca and P or Si. Cu electrodes had an orange to dark brown thin scale with blue green spots. Small pits were consistently observed mostly in the centre of such blue green spots which were identified as copper carbonates. The Pb electrodes visually showed a thin shiny transparent film with a surface very similar to the unexposed electrodes. Numerous pits were visually for pH controls and not seen for inhibitors; but SEM revealed that all electrodes had pits but the inhibitors reduced number and size of pits compared with pH controls. Thin hexagonal hydrocerussite plates were observed to occur in distinct growth areas and the presence of P or Si inhibitor seemed to increase the occurrence of hydrocerussite. Both Fe & Pb release were mostly in the particulate form while Cu release was mostly in the dissolved form. Total and dissolved Fe, Cu and Pb release models using EN parameters were developed by nonlinear regression. Fe release increased with localized corrosion (PF) and the EN model predicts that Fe release can be effectively controlled to the same degree by pH elevation or inhibitors. Cu release increased with general corrosion (LPRCR) and was also influenced by localized corrosion (ECNCR). However general corrosion was more significant for copper release which was mostly in the dissolved form. Pb release was depended on both general corrosion (LPRCR & HMCR) and localized corrosion (PF). The EN models predict that both Cu and Pb release is highest for pH control and all inhibitors reduced Cu and Pb release, which is consistent with the data. Inhibitors ranked by increasing effectiveness for reducing both Cu and Pb release are pH elevation, Si, ZOP, OP and BOP. EN monitoring is faster and less labor intensive than water quality monitoring and represents a significant advance for controlling metal release in drinking water distribution systems. The EN models were found to be comparable to water quality models developed from this study for metal release, and since EN is a real-time technique it offers a tremendous advantage over traditional water quality sampling techniques. Remote access of EN monitoring equipment is possible and the system requires little to no maintenance with the exception of a power supply or battery. The rapid turn around of corrosion rates from EN can be used to estimate metal release in drinking water proactively and mitigating measures can be implemented before the full adverse impacts are realized.

In this study, the bacterial growth dynamics of 14 pilot drinking water distribution systems were studied in order to observe water quality changes due to corrosion inhibitor addition. Empirical models were developed to quantity the effect of inhibitor type and dose on bacterial growth (biofilm and bulk water). Water and pipe coupon samples were taken and examined during the experiments. The coupons were exposed to drinking water at approximately 20°C for at least 5 weeks to allow the formation of a measurable quasi- steady-state biofilm. Bulk water samples were taken every week. In this study, two simple but practical empirical models were created. Sensitivity analysis for the bulk HPC model (for all 14 of the PDSs) showed that maintaining a chloramine residual at 2.6 mg/L instead of 1.1 mg/L would decrease bulk HPC by anywhere from 0.5 to 0.9 log, which was greater than the increase in bulk HPC from inhibitor addition at 0.31 to 0.42 log for Si and P based inhibitors respectively. This means that maintaining higher residual levels can counteract the relatively modest increases due to inhibitors. BF HPC was affected by pipe material, effluent residual and temperature in addition to a small increase due to inhibitor addition. Biofilm density was most affected by material type, with polyvinyl chloride (PVC) biofilm density consistently much lower than other materials (0.66, 0.92, and 1.22 log lower than lined cast iron (LCI), unlined cast iron (UCI), and galvanized steel (G), respectively). Temperature had a significant effect on both biofilm and bulk HPC levels but it is not practical to alter temperature for public drinking water distribution systems so temperature is not a management tool like residual. This study evaluated the effects of four different corrosion inhibitors (i.e. based on either phosphate or silica) on drinking water distribution system biofilms and bulk water HPC levels. Four different pipe materials were used in the pilot scale experiments, polyvinyl chloride (PVC), lined cast iron (LCI), unlined cast iron (UCI), and galvanized steel (G). Three kinds of phosphate based and one silica based corrosion inhibitors were added at concentrations typically applied in a drinking water distribution system for corrosion control. The data showed that there was a statistically significant increase of 0.34 log in biofilm bacterial densities (measured as HPC) with the addition of any of the phosphate based inhibitors (ortho-phosphorus, blended ortho-poly-phosphate, and zinc ortho-phosphate). A silica based inhibitor resulted in an increase of 0.36 log. The biological data also showed that there was a statistically significant increase in bulk water bacterial densities (measured as heterotrophic plates count, HPC) with the addition of any of the four inhibitors. For bulk HPC this increase was relatively small, being 15.4% (0.42 log) when using phosphate based inhibitors, and 11.0% (0.31 log) for the silica based inhibitor. Experiments with PDS influent spiked with phosphate salts, phosphate based inhibitors, and the silicate inhibitor showed that the growth response of P17 and NOx in the AOC test was increased by addition of these inorganic compounds. For this source water and the PDSs there was more than one limiting nutrient. In addition to organic compounds phosphorus was identified as a nutrient stimulating growth, and there was also an unidentified nutrient in the silica based inhibitor. However since the percentage increases due to inhibitors were no greater than 15% it is unlikely that this change would be significant for the bulk water microbial quality. In addition it was shown that increasing the chloramines residual could offset any additional growth and that the inhibitors could help compliance with the lead and copper rule. However corrosion inhibitors might result in an increase in monitoring and maintenance requirements, particularly in dead ends, reaches with long HRTs, and possibly storage facilities. In addition it is unknown what the effect of corrosion inhibitors are on the growth of coliform bacteria and opportunistic pathogens relative to ordinary heterotrophs. A method was developed to monitor precision for heterotrophic plate count (HPC) using both blind duplicates and lab replicates as part of a project looking at pilot drinking water distribution systems. Precision control charts were used to monitor for changes in assay variability with time just as they are used for chemical assays. In adapting these control charts for the HPC assay, it was determined that only plate counts ≥ 30 cfu per plate could be used for Quality Assurance (QA) purposes. In addition, four dilutions were used for all known Quality Control (QC) samples to insure counts usable for QC purposes would be obtained. As a result there was a 50% increase in the required labor for a given number of samples when blind duplicates and lab replicates were run in parallel with the samples. For bulk water HPCs the distributions of the duplicate and replicate data were found to be significantly different and separate control charts were used. A probability based analysis for setting up the warning limit (WL) and control limit (CL) was compared with the method following National Institute of Standard and Technology (NIST) guidelines.

The impact of blended orthophosphate (BOP) inhibitor addition on the corrosion of iron, copper, and lead in drinking water distribution systems was studied under changing water quality environment. Release of iron, copper, and lead were monitored at varying inhibitor doses and changing blends of source waters (groundwater, surface water, and desalinated water). Solid corrosion products on pipe surfaces under BOP treatment were evaluated with surface characterization techniques. Performance of the BOP inhibitor was compared to other corrosion control strategies. Iron scales for iron and galvanized steel coupons incubated in different blended waters in the presence of BOP inhibitor were analyzed by X-ray Photoelectron Spectroscopy (XPS) for surface composition. Identified iron corrosion products were ferric oxide (Fe2O3), magnetite (Fe3O4), and hydrated ferric oxide (FeOOH), in addition to ferric phosphate (FePO4) on coupons exposed to BOP inhibitor. Variations of water quality did not significantly affect the distribution of solid iron forms on surface films. Thermodynamic modeling indicated siderite (FeCO3) was the controlling solid phase of iron release. XPS indicated addition of BOP inhibitor produced a solid phosphate film in the iron scale which could inhibit iron release. Impact of BOP, orthophosphate, and pH adjustment on iron release in a distribution system was examined. Iron release was sensitive to water quality variations (alkalinity and chloride) associated with source and blends of finished water. Finished waters with high alkalinity content (between 149 and 164 mg/L as CaCO3) consistently mitigated iron release regardless of inhibitor use. Dissolved iron constituted about 10% of total iron release. Empirical models were developed that related water quality, inhibitor type and dose to iron release. The BOP inhibitor minimized total iron release followed closely by increasing pH (between 7.9 and 8.1), while orthophosphate dose did not affect iron release. Temperature (ranged from 21.2 to 25.3) had limited influence on iron release with BOP treatment. Monitoring copper release showed that dissolved copper was the dominant form in the effluent, at about 88%. BOP inhibitor doses of 0.5 to 2.0 mg/L proved beneficial in controlling copper concentrations to an average of below 0.5 mg/L. Control of copper release improved with increasing BOP dose, despite changes in alkalinity. Elevation of pH by 0.3 unit beyond pHs (between 7.9 and 8.1) resulted in noticeable decrease in copper concentrations of about 30%, but was more sensitive to higher alkalinity (146 to 151 mg/L as CaCO3) than BOP treatment. Developed empirical models confirmed the importance of BOP inhibitor dose, pH increase, and alkalinity content on copper release. Statistical comparison of the corrosion control strategies proved the advantage of BOP inhibitor, at all doses, over pH elevation in controlling copper release. The BOP inhibitor mitigated lead release below action level, and consistently outperformed pH elevation, in all water quality conditions. XPS analysis identified lead dioxide (PbO2), lead oxide (PbO), cerussite (PbCO3), and hydrocerussite (Pb3(CO3)2(OH)2) as the corrosion products in the scale of lead/tin coupons exposed to BOP inhibitor. XPS and Scanning Electron Microscopy (SEM) analysis suggested cerussite or hydrocerussite is the controlling solid phase of lead release. Thermodynamic models for cerussite and hydrocerussite grossly over predicted actual concentrations. Solubility and equilibrium relationships suggested the possibility of a lead orthophosphate solid that would describe the effectiveness of BOP inhibitor, although no lead-phosphate solid was detected by surface analysis. BOP inhibitor appeared to have mitigated lead release by forming a surface film between lead scale and the bulk water.

In February 2014, a coal ash spill on Duke Energy's Dan River Plant in Eden, NC released approximately 39,000 tons of coal ash into the Dan River. It took approximately one week to stop the spill. Starting in February 2015, drinking water utilities using the Dan River experienced a series of taste and odor (TandO) events described as "earthy" or "musty". Similar TandO events were not documented before the coal ash spill. This research attempted to understand causes of the TandO events and if the coal ash spill was connected. A variety of water quality analyses were performed on twelve sites from August 2016 to September 2017 on the Dan and Smith Rivers. The Smith River served as the control. From concentrations of coal ash indicators (particularly Ba, Sr, As, V, and Br-), there was a signature of coal ash on the Dan River that was not present on the Smith River. The signature could not be attributed to the coal ash spill, as the signature was present upstream of the spill. Chronic ecosystem toxicity due to metals was low and not significantly different between the Dan and Smith Rivers. No substantial TandO events occurred during the period of this study. All monitored odorants were detected with varying frequencies in both the Dan and Smith Rivers. No significant change in odorant concentration was found above and below the location of the coal ash spill. / MS

<p dir="ltr">The frequency and intensity of wildfires occurring at the wildland-urban interface is increasing, and public drinking water systems operating in these communities are at risk. Widespread volatile organic compound (VOC) and semi-VOC (SVOC) contaminations have been detected in water distribution systems, often at concentrations above regulatory limits. Uncertainty about the source and fate of these contaminants has hindered recovery efforts. It is hypothesized that one source of the contaminants is the thermal degradation of plastic components within water distribution systems. Plastics are commonly used for water conveyance due to their low cost and ease of installation. However, plastics are vulnerable to thermal degradation, and have been shown to release VOC/SVOCs into the air when thermally degraded. Further, certain plastics such as polyethylene, are vulnerable to organic compound permeation, which could result in the contamination of otherwise undamaged components. This dissertation is comprised of four studies aimed at evaluating if plastic components within water distribution systems may be a source of contamination post-wildfire.</p><p dir="ltr">First, the aqueous leaching from commercial drinking water pipes was evaluated following thermal degradation in air. In this work, eleven plastic drinking water pipes were exposed to elevated temperatures (200°C to 400°C), and subsequently submerged in water or in <i>n</i>-hexane to observe the extent of VOC leaching. Results indicated that thermally damaged drinking water pipes can be sources of VOC leaching, with ten of the eleven materials leaching benzene, a carcinogen, into water. As exposure temperature increased, there was an increase in VOC leaching from the polyethylene plastics. Conversely, in the vinyl plastics the significant mass loss associated with high exposure temperature was inversely proportional to the amount of leaching that was observed.</p><p dir="ltr">The second study determined how the direct contact of water during plastic thermal degradation impacts the formation and aqueous leaching. Experiments were carried out using a continuously stirred tank reactor (CSTR) to expose plastics to a range of temperature (100°C to 300°C) in the presence of water. Five polyethylene materials were tested, including three cross-linked polyethylene (PEX) pipes, one high-density polyethylene pipe (HDPE), and one HDPE resin. Following degradation, clean water was pumped through the reactor to evaluate the efficacy of flushing to remove contaminants from thermally damaged plastics. Again, material type and exposure temperature impacted the leaching profile. Flushing removed contaminants from the thermally damaged plastics, however the removal rate varied based on chemical properties. Exhumed materials from wildfire impacted water systems were extracted in water to assess similarities and leached up to twelve different compounds, seven of which were also detected in laboratory experiments.</p><p dir="ltr">The third study investigated the impact of polyethylene formulation on aqueous leaching following thermal degradation to further understand the underlaying phenomenon causing the formation and leaching of contaminants. The impact of resin density, antioxidant type (Irganox 1010^® or Irgafos 168^®), antioxidant dose (0 to 10 wt. %), and impact of carbon black (0 or 2 wt. %) was investigated by compounding 12 different composites and thermally degrading them in the CSTR reactor described previously. Results found that all variables tested impacted the observed leaching. The addition of antioxidants decreased the observed leaching of polyethylene degradation products but increased the leaching of a variety of antioxidant degradation products. Carbon black was found to interact with the antioxidants during compounding, leading their consumption, and as a result decreased their effectiveness in protecting the polymer chain.</p><p dir="ltr">Lastly, the susceptibility of plastic water supply connectors such as ice-maker lines, faucet connectors, and washing machines hoses was assessed. The vulnerability of rigid plastic materials within water systems has been well studied, however, water supply connectors tend to be made of flexible plastics such as plasticized PVC and low-density polyethylene, and limited data exists on the susceptibility of these materials to contamination. In this study, seven connectors were exposed to hydrocarbon contaminated water, and subsequently decontaminated by water flushing. Following an initial 24 h contamination period, water samples were collected at three consecutive periods of 72 h. Results found that all materials sorbed more than 90% hydrocarbon contaminants. All materials released contaminants into the water during decontamination, at times above health-based limits. The majority of sorbed mass remained in the plastics at the end of the decontamination periods.</p>

No / Organic matter (OM) causes many problems in drinking water treatment. It is difficult to monitor OM concentrations and character during treatment processes due to its complexity. Fluorescence spectroscopy is a promising tool for online monitoring. In this study, a unique dataset of fluorescence excitation emission matrixes (EEMs) (n = 867) was collected from all treatment stages of five drinking water treatment plants (WTPs) situated in diverse locations from subtropical to temperate climate. The WTPs incorporated various water sources, treatment processes and OM removal efficiencies (DOC removal 0%–68%). Despite these differences, four common fluorescence PARAFAC components were identified for characterisation of OM concentration and treatability. Moreover, fluorescence component ratios showed site-specific statistically significant correlations with OM removal, which contrasted with correlations between specific UV absorbance at 254 nm (SUVA) and OM removal that were not statistically significant. This indicates that use of fluorescence spectroscopy may be a more robust alternative for predicting DOC removal than UV spectroscopy. Based on the identified fluorescence components, four optical locations were selected in order to move towards single wavelength online OM monitoring.

yes / NOM deteriorates water quality by forming taste, clarification, colour, and odour problems. It also increases coagulant and chlorine consumption which can initiate disinfection by-products harmful to human health. The coagulation-flocculation (CF) technique is an established method commonly employed to remove NOM in water treatment. Plant-based coagulant products (PCPs) derived from plants like the Moringa oleifera (MO) Strychnos potatorum Linn and Opuntia ficus indica, have been studied and proposed as sustainable alternatives to chemical coagulant, like, aluminium sulphate due to their abundant availability, low cost, low sludge volume and disposal cost, and biodegradability. This review paper provides an overview of the most widely studied plant-based coagulants and discusses their NOM and turbidity removal. It investigates recent analytical tools applied in their characterisation and floc morphological studies. The paper also investigates the effects of operating parameters such as coagulant dose, temperature, and pH, on NOM and turbidity removal. It also reviews up-to-date PCPs biophysical properties and CF mechanism and examines the efficiency of their extraction methods in reducing NOM. Finally, it discusses and suggests ways to overcome commercialisation draw-back caused by nutrient addition.