MESHWR / Department of Hydrology and Water Resources / Water borne diseases due to inadequate and unsafe drinking water is a global challenge that has led to a significant number of deaths and illnesses reported annually. These diseases are prevalent in less-developed countries, especially in rural areas where there is shortage of basic infrastructure and inadequate funds for piped water systems in individual households. Community members are forced to resort to collecting water from communal water points and later storing the water in containers for daily use. Recontamination of microbiologically safe drinking water during and after collection from the water source has been recognised as a problem; hence treating water at household level is one way to provide potable water for affected communities. The microbiological quality of household water may be improved by using point-of-use treatment technologies such as chemical disinfection, solar disinfection and ceramic water filters. Some of these technologies are expensive, less effective and difficult to implement in rural communities. This research thus focused on ceramic water filters and finding an appropriate method for silver application so as to produce filters that are effective in both the provision of clean drinking water and the release of silver levels that are safe for human consumption. An assessment of the efficiency of ceramic water filters made with silver nitrate as point-of -use water treatment device in Dertig Village, North West Province, South Africa was carried out. During production of filters made with silver nitrate, the filters undergo firing in an electric kiln and ionic silver is reduced to metallic nanopatches dispersed throughout the porous ceramic media. Both filters made with silver nitrate and conventional silver nanoparticles impregnated ceramic water filters were manufactured at the PureMadi Dertig Ceramic Filter Facility, South Africa. Resulting filters were evaluated and quantified for total coliform and E. coli removal as well as silver concentration in the effluent. Ceramic water filters made with silver nitrate had a high removal efficiency for total coliforms (94.7%) and E. coli (99.3%). A comparison of the performance of filters made with silver nitrate and silver nanoparticles in the provision of potable water was carried out and results showed that the different filters had similar levels of total coliform and E. coli removal, although the silver nitrate filters produced the highest average removal of 97.23% while silver nanoparticles filters produced the lowest average removal of 85.43%. Reasonable silver levels were obtained in effluent from all filters. Average effluent silver levels were 0.07±0.04mg/L, 0.6±1.10 mg/L and 0.8±1.0mg/L for 1 g, 2 g and silver nanoparticle filters, respectively (below the EPA and WHO standard of 100 mg/L). Because silver nitrate filters resulted in the lowest effluent silver concentrations, this could potentially increase the effective life span of the filter. A cost analysis of the process proved that it was cheaper to produce ceramic water filters using silver nitrate as the chemical can be purchased locally and also eliminates labour related costs. Thus, filters made using silver nitrate could potentially improve performance, reduce production costs, and increase safety of production for workers. The results obtained from this study will be applied to improve the ceramic filtration technology as point-of-use water treatment device in an effort to reduce health problems associated with microbial contamination of water stored at household level. / NRF

There has been a recent increase in the adoption of point-of-use (POU) household water filters as an alternative to untreated tap water or bottled water. POU filters certified for lead removal have recently been distributed by the hundreds of thousands in communities amid water lead crises, as a temporary solution to protect consumers from elevated water lead levels. This thesis rigorously examines the efficacy of POU lead certified filters in removing lead under a wide range of conditions, and evaluates premature clogging due to iron and associated impacts on the cost analysis of using filters instead of bottled water. In testing ten brands of POU devices against up to four different waters for lead removal, most devices consistently removed lead to below the 5 µg/L FDA bottled water standard. However, several failures were documented, including manufacturing flaws, premature clogging, and inconsistency between duplicate filters. When waters containing more difficult to treat lead particulates were synthesized, treated water often had lead concentrations greater than the 5 µg/L bottled water standard and sometimes were even over the 15 µg/L EPA action level. In some cases, less than 50% of the particulate lead was removed by the filter, thereby replicating some problems with these devices identified in the field. While POUs usually reduced water lead concentrations by at least 80%, a combination of manufacturing issues and difficult to treat waters can cause treated water to exceed expectations. Consumers often purchase POU devices to remove particles and lead in waters that also contain high iron, prompting studies to examine the role of iron on filter performance. When we exposed two brands of pour-through POUs to waters with both high lead and iron, lead removal performance was generally not compromised, as treated water typically had lead concentrations less than 5 µg/L. One case was observed in which lead passed through a set of filters at high levels in association with iron, confirming expectations that in some waters iron could cause formation of lead particulates that are difficult to remove. High levels of iron sometimes rapidly clogged the POU filters, preventing them from reaching their rated capacity and increasing operational costs and time to filter water. Specifically, 50% (3/6) of the filters tested clogged prematurely at an iron concentration of 0.37 mg/L, 66% (4/6) at 1 mg/L and 100% (6/6) at 20 mg/L. A cost analysis for POUs vs. bottled water demonstrated that in waters with higher iron, store-brand bottled water was often the more cost-effective option, especially when iron levels were significantly higher than the EPA Secondary Maximum Contaminant Level (0.3 mg/L). The lower costs of bottled water in these situations was even more apparent if consumer time was factored into the analysis. / Master of Science / There has been a recent increase in the use of household water filters as an alternative to tap water or bottled water. Filters that are certified for lead removal have recently been distributed by the hundreds of thousands in communities amid water lead crises, as a temporary solution to protect consumers from elevated water lead levels. This thesis rigorously examines the effectiveness of these filters under a wide range of conditions. When tested against up to four different waters for lead removal, most filters consistently reduced lead to below the concentrations allowed in bottled water. In cases where the filters did not perform as expected, several filter failure modes were identified, including manufacturing flaws, filter clogging, and inconsistency between duplicate filters. In addition to these failures, when a water that contained particulate lead that was difficult to filter, as little as 50% of the lead was removed. While household filters often significantly reduce water lead concentrations, a combination of manufacturing issues and difficult to treat waters can cause poor performance. In many cases, consumers purchase filters to remove particles or lead in waters that also contain iron, which caused us to investigate the effect of iron on filter performance. When two brands of pour-through filters were tested against waters with both lead and iron, lead removal performance was generally not compromised. One exceptional case was observed where both high levels of lead and iron passed through the filters, leading us to believe that iron in some waters could create conditions where lead is more difficult to remove. In many cases, the presence of iron caused filters to dramatically slow down or clog. Premature clogging due to iron prevented filters from reaching their rated capacity and, in doing so, significantly increased cost and filter times. A cost analysis for filters vs. bottled water demonstrated that in waters with higher iron, store-brand bottled water was often the more cost-effective option, especially in waters with higher levels of iron. The lower costs of bottled water in these situations was even more apparent if consumer time was factored into the analysis.

Lead enters drinking water by a process of corrosion, dissolution or particle detachment from lead bearing plumbing materials. Preventing contamination of water from lead-tin solder corrosion and achieving effective removal of particulate lead by point-of-use (POU) filters are important public health goals. These topics are especially timely given forthcoming revisions to the Lead and Copper Rule and ongoing efforts to reduce lead levels at the tap. Recently a switch from non-corrosive groundwater to a surface water source at a utility in Illinois caused unusual drinking water contamination from the release of large lead solder chunks from plumbing to water. Point-of-use (POU) filters distributed to remove the lead at this utility and elsewhere were not always completely effective. Here, we elucidate the mechanism of lead solder release in two chapters, followed by two more chapters examining lead removal by POU filters. The lead solder contamination arose after the water utility switched sources from high sulfate and low nitrate groundwater to a surface water with lower sulfate and high nitrate during runoff events. Such problems were unexpected because the surface water with high nitrate was not considered corrosive according to current theory. A chapter entitled A Novel Mechanism of Lead-Tin Solder Spallation in the Presence of Nitrate describes how 1) nitrate is extremely corrosive to lead:tin solder galvanically connected to copper, 2) nitrate corrosion can sometimes cause detachment of solder chunks to water, and 3) nitrate corroded the metal by reduction to ammonia and other reaction products. Another Chapter reports a follow up study, that reproduced the essence of nitrate induced spallation corrosion as observed in homes, using copper pipe with beads of lead-tin solder attached. During a 4-month experiment, the non-corrosive groundwater with high sulfate caused no solder beads to detach and only about 1% of the total lead was released to water. But in the surface water with high nitrate believed to cause the lead problem, 100% of the solder beads detached after just two months, and 80% of the total lead in the solder was released to water after 4 months. In the same surface water that had lower nitrate, with or without zinc orthophosphate or polyphosphate inhibitors, only 8 to 17% of the solder beads detached. Electrochemical studies also found that equimolar concentrations of chloride did not cause the disintegration of tin solder or as much weight loss as nitrate. Moreover, sulfate concentrations as low as 0.75 mM could effectively inhibit tin corrosion caused by 10 mg/L NO3-N. Studies focused on efficacy of POU filters have indicated that soluble lead in water is reliably removed, but sometimes particulate lead can escape capture and contaminate the treated water. To better understand this issue and practical limitations of filter use, field studies were performed in occupied and unoccupied homes in Enterprise, LA and New Orleans under both normal and extreme conditions of water lead contamination. For severe lead contamination present after lead pipes were disturbed or when a very long lead service line was present, and filters were tested to 200% of their rated capacity, the treated water occasionally had more than 15 ppb lead even when a very high percentage of the lead was removed. In Enterprise and New Orleans water with more typical levels of influent lead, the treated water was always below 1 ppb lead. But in Enterprise water with high iron and manganese the filters clogged quickly, causing higher costs for filtered water and consumer dissatisfaction. The occasional problems in removing particulate lead observed in this and prior research gave impetus to a series of bench-scale experiments elucidating particulate lead removal mechanisms by conventional ion-exchange media in sodium (Na+), strong acid (H+), chloride (Cl-) or strong base (OH-) form. Suspensions of lead phosphate particles of varying sizes and age revealed marked differences in dissolution rates under acidic, circa neutral and basic pHs that are caused by treatment with H+, Na +, OH -, Cl- form resin. Fresh nanoparticle lead phosphate particles were very labile, and immediately dissolved at pH 4 to form soluble Pb+2 ions which were quickly removed by strong acid media. High pHs > 10 and phosphate removal by OH– form resin could also dissolve the particles, and then remove the anionic soluble lead formed at high pHs. Na+ and Cl- resin caused little or no dissolution at the circa neutral pHs associated with their use and had lower rates of lead removal from water as a result. Older lead phosphate particles acquired from a New York City harvested lead pipe loop rig or purposefully synthesized in the laboratory, did not dissolve as readily as fresh nanoparticles which profoundly affected their relative removal efficiency by the different media. Overall, dissolution of lead phosphate particles in the ion-exchange media can sometimes have a range of important effects that can enhance or hinder lead removal dependent on circumstance. This thesis enhances our understanding of water lead contamination mechanisms by spallation of lead-tin solder and factors affecting lead removal by some POU filters. These novel insights can be helpful in preventing and mitigating future water lead contamination events. / Master of Science / Lead enters drinking water by a process of corrosion, dissolution or particle detachment from lead bearing plumbing materials. Preventing contamination of water from lead-tin solder corrosion and achieving effective removal of particulate lead by point-of-use (POU) filters are important public health goals. These topics are especially timely given forthcoming revisions to the Lead and Copper Rule and ongoing efforts to reduce lead levels at the tap. Recent studies have revealed that high nitrate sometimes causes severe lead contamination of water in homes with lead soldered copper pipe. This thesis elucidates a novel mechanism of lead solder corrosion from nitrate attack in two chapters, followed by two more chapters examining problems associated with lead removal from water by point-of-use (POU) filters. In a recent water lead contamination event, nitrate somehow caused large chunks of metallic lead solder to fall off pipes into the drinking water, a novel process that we term "spallation" corrosion. This observation inspired experiments to recreate this problem in the laboratory which found 1) nitrate and its reduced reaction products create a very low pH at the lead or tin anode during the nitrate-accelerated corrosion 2) the corrosion eats at the bond between the lead-tin solder and the copper pipe, cracking the lead:tin solder, causing chunks of metal to completely detach into water, and 3) corrosion of metal via nitrate reduction to ammonia at the tin anode. Follow-up electrochemical studies reproduced the essence of field nitrate induced spallation corrosion as seen in homes using copper pipe with beads of lead-tin solder attached. These beads detached to water during a 4-month experiment in some water chemistries and not others. No solder beads detached, and only about 1% of the total lead in the solder was released to water, during exposure to a non-corrosive groundwater with high sulfate. But all the solder beads detached in just two months, and 80% of the total lead was released to the water in 4 months, in a surface water with high nitrate. Electrochemical studies found that sulfate concentrations as low as 0.75 mM effectively inhibited the extreme tin corrosion caused by 10 mg/L NO3-N. Testing of lead certified POU filtration performance under varying conditions offers insight into challenges facing consumers. Field filtration studies were conducted in occupied homes for typical water lead challenges, or in unoccupied homes for testing of potentially dangerous water lead hazards, in Enterprise and New Orleans, LA. Results illustrate the difficulty of always achieving effective lead removal in cases where 1) the lead service line is very long, or 2) there is high erratic particulate lead after a lead service line is disturbed. Although effective lead removal occurred in other situations, the presence of very high levels of iron caused premature filter clogging and associated consumer frustration. Problems observed in removing particulate lead informed a series of bench-scale studies evaluating the role of particle age and size on filtration effectiveness by cation and anion form exchange resins (H+, Na +, OH -, Cl-). Batch tests demonstrated that fresh lead phosphate particles less than 1 micron in size are quickly dissolved at pH less than 4 caused by H+ form ion-exchange resin and were dissolved moderately fast at pH higher than 10 caused by OH- form ion-exchange resin. But the particles hardly dissolved at all at the moderate pHs present when Na+ and Cl- form resins are used. Dissolved lead was readily removed by H+, OH - and Na+ form resins at the pH range they created during treatment, but not by Cl- form resins. Lead phosphate particles from New York City did not dissolve as quickly as fresh nanoparticles, which sometimes enhanced or hindered their relative removal efficiency in the range of media tested. Overall, dissolution of lead phosphate particles within the media had important effects on the overall lead removal and could even cause previously removed lead to be released in some cases. This thesis enhances our understanding of water lead contamination mechanisms by spallation of lead-tin solder and lead removal by some POU filters. These novel insights can be helpful in preventing and mitigating future water lead contamination events.

The propagation of contaminants in the environment continues to threaten public health and safety. Conventional analytical techniques for environmental detection require centralized facilities and intensive resources for operation. An effective implementation of a wide network of field deployable point-of-use (POU) sensors can potentially enable real-time monitoring of water quality parameters and inform decision making on public health outbreaks. The use of nanotechnology and field-deployable analytical tools can potentially advance the development of POU sensors for future field application. In this dissertation, we developed environmental sensing techniques that utilize nanocomposites made of low-cost, biocompatible, and sustainable nanomaterials combined with Raman spectroscopy. First, a technology pre-assessment was performed that included a comprehensive evaluation of cellulose-derived nanocomposites and nanobiotechnology enabled techniques for their sustainable long-term environmental application. Furthermore, to contribute to the better understanding of the potential environmental implications of nanomaterial production and application, life cycle assessment (LCA) was used to evaluate the environmental impacts of six iron precursors and seven iron oxide nanoparticle synthesis methods. Secondly, in the technology development step, gold (Au) and iron oxide (Fe3O4) nanoparticles were incorporated onto bacterial cellulose nanocrystals and nanoscale magnetite were synthesized. As proof-of-concept environmental applications, the Au@Fe3O4@BCNCs were applied for the magnetic separation and surface-enhanced Raman scattering (SERS) detection of malachite green isothiocyanate (MGITC), and nanoscale magnetite were applied for phosphate (PO43-) removal and recovery from synthetic urine matrices. Finally, in the technological application step, three environmental sensing applications are presented that use nanomaterial-based sensor platforms and/or Raman spectroscopic techniques. The first application involved using Lectin-modified BCNCs coupled SERS and machine learning for discrimination of bacterial strains. The second application presents a simple Raman-stable isotope labeling approach for the study of viral infection of bacteria. The third application involved use of SERS pH nanoprobes for measuring pH in droplets of complex matrices (e.g., DMEM cell culture media, human saliva). / Doctor of Philosophy / The current generation of analytical tools for environmental detection rely upon centralized facilities and intensive resources for operation. The combination of nanotechnology and field deployable analytical tools can aid in the development of point-of-use (POU) sensors for field monitoring of environmental contaminants. In this dissertation, we combined low-cost, biocompatible, and sustainable nanomaterials with Raman spectroscopy-based techniques to develop potentially field-deployable environmental sensing techniques. First, a technology pre-assessment was performed which involved a comprehensive evaluation of cellulose-derived nanocomposites and nanobiotechnology enabled techniques for their sustainable long-term environmental application. Furthermore, life cycle assessment (LCA) was used to evaluate the environmental impacts of iron oxide nanoparticle synthesis methods to better understand environmental impacts of nanoparticle production. Secondly, in the technology development step, we developed the nanocomposites: Au and Fe3O4 nanoparticles incorporated bacterial cellulose nanocrystals and nanoscale magnetite. As proof-of-concept environmental applications, the Au@Fe3O4@BCNCs were used for the detection of malachite green isothiocyanate (MGITC), and the nanoscale magnetite were used for phosphate (PO43-) removal and recovery from synthetic urine. Finally, in the technological application step, (1) selective detection of bacteria was performed using lectin-modified BCNCs as SERS biosensors coupled with SERS and machine learning. (2) Viral infection of bacteria was evaluated using Raman spectroscopy and Deuterium isotope labeling, and (3) pH in micro-droplets of DMEM cell culture media and human saliva were observed using SERS pH nanoprobes.

Per- and polyfluoroalkyl substances (PFAS) are a class of man-made contaminants of increasing human health concern due to their resistance to degradation, widespread occurrence in the environment, bioaccumulation in human and animal organ tissue, and potential negative health impacts. Drinking water is suspected to be a primary source of human PFAS exposure, so the US Environmental Protection Agency (US EPA) has set interim and final health advisories for several PFAS species that are applicable to municipal water supplies. However, private drinking water supplies may be uniquely vulnerable to PFAS contamination, as these systems are not subject to EPA regulation and often include limited treatment prior to use for drinking or cooking. The goal of this study was to determine the incidence of PFAS contamination in private drinking water supplies in two counties in Southwest Virginia (Floyd and Roanoke), and to examine the potential for reliance on citizen-science based strategies for sample collection in subsequent broader sampling efforts. Samples for inorganic ions, bacteria, and PFAS analysis were collected on separate occasions by homeowners and experts at the home drinking water point of use (POU) in 10 Roanoke and 10 Floyd County homes for comparison. Experts also collected an outside tap PFAS sample. At least one PFAS compound was detected in 76% of POU samples collected (n=60), with an average total PFAS concentration of 23.5 parts per trillion (ppt). PFOA and PFOS, which are currently included in EPA health advisories, were detected in 13% and 22% of POU samples, respectively. Of the 31 PFAS species targeted, 15 were detected in at least one sample. On average, a single POU sample contained approximately 3 PFAS, and one sample contained as many as 8 different species, indicating that exposure to PFAS in complex mixtures is worth noting. Although there were significant differences in total PFAS concentrations between expert and homeowner collected samples (Wilcoxon, alpha = 0.05), it is unclear whether this difference was due to contamination by the collector or the water usage and time of day of sampling (i.e. morning, afternoon). It is worth noting that there was no significant difference in the number of PFAS species in the samples collected by homeowners and experts. Given the considerable variation in PFAS detections between homes, future studies reliant on homeowner collection of samples appears possible given proper training and instruction to collect at the same time of day (i.e. first thing in the morning). / Master of Science / Per- and polyfluoroalkyl substances (PFAS) belong to a large family of manmade compounds that are commonly used in a variety of household and consumer products due to their unique water and stain resistant properties. PFAS compounds are not easily broken down in the environment and have been detected globally in air, soil, and water samples. In addition to their environmental detections, PFAS are slow to be removed from the body after ingestion and known to cause negative health effects in concentrations less than one part per trillion. Drinking water is considered to a main source of PFAS consumption for humans; as such, the US Environmental Protection Agency (US EPA) has set strict, but not legally binding, interim and final health advisories (HA) for four types of PFAS. However, these health advisories only apply to public water services and do not cover private drinking water systems, such as wells or springs, which are the full responsibility of the well owner. Private drinking water system users often do not treat their water before drinking which may make these systems uniquely vulnerable to PFAS contamination. This study focused on 20 total homes, 10 in Roanoke County and 10 in Floyd County to see if PFAS was present and to determine whether or not homeowners would be able to collect their own samples for PFAS analysis at home as accurately as researchers or experts with proper instructions. Homeowners and experts collected drinking water samples inside at a point of use (POU), usually at a kitchen faucet, and outside of the home, usually from a tap. PFAS were present in 76% (n=60) of POU samples, with an average combined concentration of 23.5 parts per trillion (ppt). The two most well studied PFAS, PFOA and PFOS were detected in 13% and 22% of POU samples, respectively. It was also common to detect at least 3 PFAS in a single sample. Although there were differences in total average concentrations of PFAS in samples collected by homeowners and experts, variation could be caused by several factors indicating that with proper training and instruction it is likely future studies could still rely on homeowners to collect samples for PFAS analysis.