Brass components are widely used in drinking water distribution systems as valves, faucets and other fixtures. They can be corroded by "dezincification," which is the selective leaching of zinc from the alloy. Dezincification in potable water systems has important practical consequences that include clogged water lines, premature system failure and leaks, and release of contaminants such as lead. Brass failures attributed to dezincification are known to occur at least occasionally all over the world, and have emerged as a significant problem in the U.S. recently due to the use of inexpensive high zinc brass fittings in cross-linked polyethylene (PEX) plumbing systems. As PEX systems gain popularity and leaded brass is recognized as an important source of lead in potable water systems, it is important to examine dezincification corrosion in more detail. An in-depth literature review revealed that conventional wisdom about dezincification was no longer adequate in explaining failures observed in modern water systems. Little research has been conducted since the landmark work of Turner et al. nearly half a century ago. The potential role of chloramines, phosphate inhibitors, and modern understanding of water chemistry need evaluation. The role of physical factors including stirring, heating and galvanic connections are also potentially influential. A mechanistic study of zinc solubility and corrosion of copper: zinc couples provided insight to factors that might mitigate and exacerbate zinc leaching from brass. Zinc solubility and corrosion was reduced by higher pH and bicarbonate, but was enhanced by higher chloride. Hardness ions including Mg⁺² and Ca⁺² had little effect. Alloys with higher zinc content had a greater propensity for dezincification corrosion. Stirring and galvanic connections caused brass to leach more metals and have higher weight loss. Heating may contribute to corrosion scale accumulation. A comprehensive examination of dezincification as a function of water chemistry used numerous techniques that include measurement of galvanic currents, metal leaching, and weight loss. In general, as would be predicted based on results of the study of solubility and corrosion of pure zinc, chloride emerged as an aggressive ion whereas bicarbonate was beneficial to brass corrosion. Hardness had little impact, and phosphates, silicates and Zn+2 inhibitors had a significant short-term benefit but little long-term benefit. The relationship between dezincification corrosion, lead leaching from brass, and water chemistry was investigated in Chapter 5. Surprisingly, lead and zinc leaching from a range of brasses were found to be negatively correlated. Hence, use of brasses that minimize dezincification problems might increase lead leaching. This thesis represents a comprehensive analysis of factors that are influential for dezincification and lead leaching from brass in premise water distribution systems through literature reviews, mechanistic investigations, bench-scale experiments, and case studies. Results can be used by water utilities, plumbing engineers, manufacturers and home owners to better prevent, recognize, and mitigate brass and dezincification corrosion problems. / Master of Science

The increasing demand for low carbon technology has increased the demand for some critical materials. Graphite is one of the strategic raw materials defined by the European Union as it is used in the production of for example batteries in electrical vehicles. Natural graphite is extracted through mining and the production is currently located outside the European Union. However, natural graphite deposits exist in for example Sweden. Mining activities can cause environmental issues, e.g. release of metals to the environment. By studying sediment in lakes, the historical element load can be investigated. In the Vittangi area (northern Sweden), a graphite deposit is located close to the natural lake Hosiojärvi. In the area, exploration has been conducted during the last 100 years. The latest exploration was conducted by the company Talga, who is also planning to extract the graphite. The aim of this master thesis is to determine the geochemical processes affecting the mobility of Co, Cu, Ni and Zn in Hosiojärvi, as well as their historical accumulation in the lake. Due to previous exploration in the area, the eventual impact from trace elements related to the bedrock and graphite deposit has also been studied. Based on previous elemental load to the sediment, the future impact until the mine starts have been discussed. The method used for answering the questions have been sampling of sediment, analysing metal concentrations in surface water, groundwater and sediment and dating of the sediment to determine sediment accumulation rate. The study shows that there has been an increase of Co, Ni and Zn to the lake, as the concentrations in the sediment has increased in the upper parts. By looking at those elements, the increase could be explained by the exploration during 1960 – 1970. The sediment is assumed to be in reduced conditions and the zone where redox processes can occur is assumed to be in the interface between the bottom water and the top sediment. In the sediment, framboidal pyrite is formed in the upper and lower parts of the sediment. Analysis on surface water shows that during the last four years, there is an increasing trend of  Co, Ni, Zn and SO4. The groundwater flows through the mineralisation and affects the water quality in Hosiojärvi, as the water quality of the lake has become more similar to the groundwater. The overall conclusion of the study is that the lake has been impacted by the previous exploration and is assumed to continue being affected until the planned mine is starting to operate.

Aging and leaking water infrastructure wastes water resources and creates public health risks. Upgrading of potable water systems represents a large financial burden for water utilities and private property owners. The conventional approaches of repair, rehabilitation and replacement are very effective, but will take decades to implement even if a financial commitment to do so was made immediately. A novel approach of in-situ remediation of leaks, achieved by harnessing the ability of water or pipe to repair leaks via clogging, could potentially reduce leak rates and extend the lifetime of existing infrastructure at relatively low cost and inconvenience. Physical clogging, precipitation and metallic corrosion were identified as major mechanisms of in-situ leak remediation in potable water pipelines. Autogenous repair (i.e., self-repair without added particles) of small leak-holes (150–"1000 μm) in copper and iron was validated in the laboratory at water pHs of 3.0–11.0, operating water pressures of 20–60 psi, upward and downward leak orientations, and for a range of water chemistries. In bench scale experiments, the time to repair of iron pipe leaks increased with leak size to the power of 0.89–1.89, and decreased with pipe wall thickness to the power of -1.9 to -1.0. The time to repair of copper pipe leaks increased with water pressure to the power of 1.7. Additionally, the waters with a higher DO and corrosivity as measured by RSI, significantly decreased the time to repair of carbon steel 400 μm leaks by 50–70%. The presence of chlorine dioxide significantly increased the fraction of repaired 200 μm copper pipe leaks by 3 times when compared to the control without any disinfectant. In the building scale study, the fraction of repaired iron pipe leaks decreased with the logarithmic leak size with a slope of -0.65 after one-year duration of experiments, while leak orientation and water pressure were not influential in time to or likelihood of repair for iron pipe leaks. Addition of calcium carbonate particles (~8.8 μ]m), silica particles (~29 μm) and wood ash particles (~160 μm) in Blacksburg, VA tap water at a water pressure of 10 psi increased the fraction of remediated iron pipe leaks of 280–1000 μm diameter sizes. Although the control condition with no added particles for 58 days resulted in remediation of 0/12 leaks, remediation rate increased to 1/12 with calcium carbonate particles, to 10/12 with silica particles and to 10/12 with wood ash particles. Leak size and particle size played an important role in controlling the remediation success rate. The strength of the in-situ leak repair was sometimes very strong and resilient. The sealing materials of leak-holes repaired at 20–60 psi could sometimes withstand a 100 psi water pressure without failure, demonstrating the potential of the approach to sustain aging and leaking infrastructure. In-situ leak repair can also occur naturally, and the success rate might be unintentionally altered by adjustment of chemistry or treatments that decrease or increase particulates. / Ph. D. / Old and leaking pipes waste water resources and can contaminate water. Upgrading of drinking water systems represents a large financial burden for water utilities and home owners. The traditional approaches to repair or replace the leaking water pipes are very effective, but will take decades to implement even if a financial commitment to do so was made immediately. A new approach of leak remediation, achieved by changing the drinking water chemistry, could potentially reduce leak rates and repair water leaks while in use without digging up the buried water pipes. Therefore, leak remediation could extend the lifetime of existing infrastructure at relatively low cost and inconvenience, and may be necessary if society cannot afford pipe replacement. Recent field observations indicate that metal corrosion, one type of reaction that eats up water pipes and causes water leaks, could clog the leaks via the corrosion products. And the repair in most cases could last for a long period of time. Our work was the first to reproduce the field observations in the laboratory, revealing that water pipe leaks could be successfully clogged or remediated by natural corrosion reaction products, if the water chemistry is favorable. Additionally, our work also showed that water leaks could be clogged or remediated by addition of water particles to drinking water, which was practiced by Roman engineers a long time ago. There are legitimate health concerns about particulates because they are indicative of microbial risks, but addition of particulates to water at low levels might heal pipes without such concerns. We also proved that in some cases the repaired materials clogging the leaks could withstand a very high household water pressure, showing that the sealing materials in water leaks repaired with natural corrosion products or added water particles could create long term repairs. With improved practical understanding this approach might be usefully applied, either intentionally to repair existing leaks, or make sure that changes to water chemistry do not unintentionally make problems worse.

Understanding and limiting public health threats resulting from exposure to opportunistic pathogens (OPs) in domestic water (i.e., hot/cold water for human use) will be one of the grand challenges for water safety in the 21st century. This dissertation anticipates some of the complexities in balancing stakeholder goals and developing building standards to limit OP growth, and advances scientific understanding of OP survival and proliferation in domestic plumbing systems. In a cross-sectional survey of water- and energy-efficient buildings, domestic water age ranged from 8 days to 6 months and resulted in pH and temperature fluctuations, rapid disinfectant residual decay up to 144 times faster than municipal water delivered to the buildings, and elevated levels of OP gene markers. This motivates future work to determine how to maintain high quality and safe water while preserving the sustainability goals of these cutting-edge buildings. Head-to-head pilot-scale experiments examining OP growth in recirculating hot water systems revealed that elevated temperature had an overarching inhibitory effect on L. pneumophila growth where temperatures were maintained. However, control was undermined in distal branches, especially when density-driven convective mixing gradients maintained ideal growth temperatures and delivered nutrients to the otherwise stagnant branches. These results resolve discrepancies reported in the literature regarding the effects of flow, and identify important system design and operational conditions that facilitate OP growth. Advancements were also made in understanding how corrosion can trigger OP growth. In Flint, MI, corrosive Flint River water damaged iron pipes, releasing iron nutrients, consuming chlorine residual, and supporting high levels of L. pneumophila in large building systems. This likely triggered two unprecedented clusters of Legionnaire's disease. In pilot-scale systems, copper released from copper pipes, but not dosed as soluble cupric, triggered release of >1,100 times more H2 into the water due to deposition corrosion. The organic carbon fixed by autotrophic hydrogen oxidation has the potential to facilitate OP growth, but more work is needed to understand the limits of this mechanism. Finally, well-controlled laboratory experiments confirmed past reports from field surveys that the use of chloramines trigger a trade-off between controlling Legionella and allowing non-tuberculous Mycobacteria to persist. / Ph. D. / Understanding and limiting public health threats resulting from exposure to opportunistic pathogens (OPs) in domestic water (i.e., hot and cold water intended for human use) will be one of the grand challenges for water safety in the 21st century. Unlike traditional fecal-based waterborne pathogens that have all but been eliminated through advanced treatment applied at water treatment facilities, OPs are native microbial members of drinking water and tend to proliferate in domestic plumbing. In addition to the complexity and technical nature of engineering controls applied in buildings to limit OP growth, there are many stakeholder groups with varied responsibilities and expertise in preventing, diagnosing, and/or remediating problems. Stakeholders sometimes present additional challenges when their goals have direct or indirect trade-offs with limiting OP growth in buildings. This dissertation anticipates some of the challenges to come, and advances scientific understanding of how OPs survive and proliferate in domestic plumbing systems. Water- and energy-efficient buildings, while nobly seeking to preserve precious natural resources, potentially create unintended consequences with respect to water quality. In a cross-sectional survey of green building designs, water remained within domestic plumbing for over a week to months before being used by consumers, and resulted in water quality changes that facilitated the growth of OPs. While short-term solutions exist, such as flushing water to decrease water stagnation and introduce “fresh” water into the system, this work motivates future research for how to maintain high quality and safe water while preserving the sustainability goals of these cutting-edge buildings. Systematic experiments were conducted on water heaters with a recirculating pump, which are marketed as a “green” technology for water and energy savings, to determine the effect of system design and operation on the growth of OPs. Elevated temperature was found to have an overarching inhibitory effect on growth of <i>L. pneumophila</i>, the most commonly reported OP. However, when the water heater temperature was not sufficient to completely eliminate <i>L. pneumophila</i> (51 °C), higher water temperatures actually supported high levels of <i>L. pneumophila</i> growth in infrequently used pipes by periodically disinfecting other microorganisms that are more susceptible to thermal disinfection and decreasing competition for nutrients. System design also impacted <i>Legionella</i> growth. In pipes that slowly mixed with the recirculating line (simulating a pipe running upward to a shower head from a recirculating line in the floor, for instance), <i>L. pneumophila</i> were consistently elevated relative to pipes that did not convectively mix (simulating a pipe running downward to a kitchen tap from a recirculating line in the ceiling, for instance). The slow mixing maintained ideal <i>Legionella</i> growth temperature in the pipes with mixing, even when water heaters were maintained well above thermal disinfection levels for <i>Legionella</i> (i.e., at 60 °C). This is due to continuous delivery of nutrients to the upward pipes with mixing, but not the downward pipes without it. This result is significant because it outlines scenarios encountered in real buildings where even the most effective thermal disinfection strategy can be undermined in distal branches within the building. This work also outlines the importance of corrosion in potentially triggering OP proliferation. In Flint, MI, when the water utility began distributing very corrosive Flint River water, the new water source damaged iron water pipes, releasing iron (which is a nutrient for <i>Legionella</i>) and eliminating disinfectant residual in the distribution system (which is needed to prevent <i>Legionella</i> regrowth). As a result, the corrosion supported increased <i>Legionella</i> levels and likely triggered two unprecedented clusters of Legionnaires’ disease. In the pilot-scale systems, corrosion of the water heater anode rod caused trace nutrients to evolve into the water. However, this only occurred when low levels of copper released to the water from the natural corrosion of copper pipes were present. Ionic copper, which is sometimes used to disinfect <i>Legionella</i>, did not have the same effect when it was dosed to the experiment at similar concentrations. These trace nutrients generated from copper-enhanced corrosion of the water heater anode rod are a potential source of carbon for OP growth, and may help explain the variable effects of copper that have been reported in the literature. More work is needed to fully understand this potential growth mechanism. Finally, this work confirmed past field observations that there is a trade-off between controlling <i>Legionella</i> and allowing <i>Mycobacteria</i>, another OP, to persist when using chloramines disinfectant residual. Reproducing this phenomenon in controlled laboratory settings is an important step in understanding, and ultimately preventing it.

published_or_final_version / abstract / Geography and Geology / Master / Master of Philosophy

This work examines the hydrogeochemical evolution of Tucson basin groundwater, including isotope hydrology, geochemistry and age determinations. Results of mineralogic investigation on basin fill were used to constrain water-rock geochemical reactions. Examination of 45 years of water quality data shows that groundwater mining has affected water quality. Stable isotopes of carbon, oxygen, hydrogen, sulfur, and chlorine and radiocarbon, tritium and radon determinations refine the interpretation of hydrogeochemical evolution of Tucson basin groundwater as modelled with NETPATH. Two distinct sampling periods, the first in 1965 and the second between 1984 and 1989, resulted in the determination of groundwater ages for water mined two decades apart. Isotope hydrology and geochemical modelling suggest that much of the water presently mined from the Tucson basin has a component recharged during the last 50 years. Increased sulfate concentrations suggest that heavy pumping in the northeastern basin may have induced increased leakage from lower units. Results of geochemical modelling indicate an average of 5 percent mountain-front recharge to the Ft. Lowell Formation along the northern aquifer margin. An increase in dissolved solids along the basin margin implies that this component to recharge has increased in the past decade. The radiocarbon age of the basin groundwater was compared with the temporal movement of water as modelled with MODFLOW and PATH3D. In general, the hydrologic simulation agrees with both the distribution of tritium and the exponentially modelled water age, as determined with bomb-derived radiocarbon, for areas of the Tucson basin that contain water less than 50 years in age. Hydrologic modelling failed to predict the antiquity of recently sampled water in the central basin but is similar to age determinations on waters collected in 1965.

Both instantaneous current and chemical propagation predictions are of utmost importance for all littoral naval operations, including diving, amphibious and mine warfare ones. Undoubtedly, the operating limits and environmental thresholds are crucial and highly reliant on the accuracy and precision of the predictions. San Diego Bay is important because it hosts a large part of the U.S. fleet and has special ecological significance. A hydrodynamic model, "Water Quality Management and Analysis Package" (WQMAP), is used to predict the instantaneous currents with various forcing functions (tides, winds, and lateral boundary fluxes) and a hydrochemical model, "Chemical Management and Analysis Package", (CHEMMAP) to predict the water contamination and to simulate chemical attacks/accidents in San Diego Bay, which raise considerations regarding public health, economy, ecology or even national security. The study shows the barotropic nature of San Diego Bay, the slight significance of wind and the vulnerability of a semi-enclosed tidal basin in a possible chemical attack or accident. Simultaneously, it evaluates and uses two models used by NAVOCEANO. / Hellenic Navy author.

West Reflex Lake is a hypersaline lake in the Canadian Great Plains. The lake contains four types of shoreline carbonate structures: isolated pinnacles, bioherms (aggregates of pinnacles), laminated coatings, and beachrock. This study investigates the processes of formation of West Reflex Lake’s shoreline carbonates. A variety of petrographic and geochemical techniques were used to characterize the texture, mineralogy, and chemistry of the carbonates. The shoreline carbonates formed as a result of biotic and abiotic precipitation at the site of saline springs that supply Ca2+ to the lake. Evidence for biologically-influenced precipitation includes strong epifluorescence, presence of micrite cements, and abundance of microbial filaments. Abiotically-precipitated cements formed due to groundwater inflow. The isolated pinnacles and bioherms formed as a result of groundwater percolating through a framework of microbial filaments, whereas the laminated coatings formed as a result of calcification of coherent microbial mats adhering to a substrate. / May 2017

Forest management practices usually preserves riparian buffers along watercourses in order to protect stream water from physical, chemical and ecological changes caused by clear-cutting. The purpose of this thesis was to investigate whether there is a relationship between the size of the riparian buffer zone along small streams, i.e., headwaters, and a number of physical and chemical attributes of these streams. Twelve headwaters in the Västerbotten county and twelve in Jönköpings county were investigated. These headwaters had a range of buffer widths from “No buffer” (no trees left), Thin buffer” (&lt; 5 m wide), to “Moderate buffer” (&gt;5 m wide) and “Reference” (no harvest) streams were also included. Tested physical and chemical conditions were light in the riparian zone, air and water temperature, stream bed cover and water chemistry. Buffer width had a significant effect on reducing light levels and temperature in the riparian zone; a buffer width over 13 m on each side of the stream was needed to maintain light and air temperature as in reference conditions. Regarding water temperature, increasing sedimentation and water quality, no significant reducing effect of increasing riparian buffer width was found.

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, in fulfilment of the requirements for the degree of Master of Science August 2017. / Streamwater chemistry is influenced by several factors that include: geology, soil-geology interactions, land use, climate change, topography, vegetation, mechanical and chemical weathering. The dominance of these factors when determining the chemistry of streamwater varies from one situation to the other. Four different catchments in the Drakensberg were monitored to identify the processes determining temporal and seasonal patterns in streamwater chemistry. The land uses of the catchment include: CP03 (previously afforested, degraded), CP04 (pristine grasslands), CP06 (pristine grasslands) and CP09 (protection from fire). All the catchments were investigated for differences in major ion concentrations, streamwater temperatures, dissolved organic carbon (DOC), dissolved oxygen, pH, conductivity. There were comparisons made between historical and recent data collected at the Cathedral Peak Research Site. Comparisons were made between CP03 and CP06 to identify effects of storm events on streamwater chemistry. CP03 and CP09 had significant statistical differences in terms of major ions. Land use and stormflow path ways were most influential in determining the streamwater chemistry across catchments. / LG2018