It has been a practice to use seawater for preparing acid in offshore operations where fresh water is relatively expensive or logistically impossible to use. However, hydrochloric acid will release calcium ion into solution, which will combine with sulfate ion in seawater (greater than 3000 ppm) and calcium sulfate will precipitate once it exceeds its critical scaling tendency. A few studies have provided evidence for this problem and how to address this problem has not been fully examined. Core flood tests were conducted using Austin Chalks cores (1.5 in. x 6 in. and 1.5 in. x 20 in.) with permeability 5 md to investigate the effectiveness of scale inhibitor. A synthetic seawater was prepared according to the composition of seawater in the Arabian Gulf. Calcium, sulfate ions, and scale inhibitor concentrations were analyzed in the core effluent samples. Solids collected in the core effluent samples were analyzed using X-ray photoelectron spectroscopy (XPS) technique and thermodynamic calculation using OLI Analyzer software were conducted to identify the critical scaling tendency of calcium sulfate at different temperatures. Results showed that calcium sulfate precipitation occurred when seawater was used in any stage during matrix acidizing including preflush, post-flush, or in the main stage. Injection rate was the most important parameter that affected calcium sulfate precipitation; permeability reduction was significant at low flow rates, while at high rates wormhole breakthrough reduced the severity of the problem. More CaSO4 precipitated at high temperatures, accounting for more significant permeability reduction in the cores. The values of critical scaling tendency at various temperatures calculated by OLI ScaleChem 4.0.3 were believed to be 2.1, 2.0, and 1.2 respectively. A scale inhibitor (a sulfonated terpolymer) was found to be compatible with hydrochloric acid systems and can tolerate high concentration of calcium (30,000 mg/l). Analysis of core effluent indicated that the new treatment successfully eliminated calcium sulfate scale deposition. The concentration of scale inhibitor ranged from 20 to 250 ppm, depending on the scaling tendencies of calcium sulfate. This work confirms the damaging effect of preparing hydrochloric acid solutions using seawater on the permeability of carbonate cores. Therefore, it is recommended to use fresh water instead of seawater to prepare HCl acids whenever possible. If fresh water is not available, then a proper scale inhibitor should be added to the acids to avoid calcium sulfate precipitation.

Phosphates are used by drinking water utilities to 1) reduce iron/manganese aesthetic problems by sequestration, 2) inhibit calcium carbonate scale formation via threshold inhibition, and 3) reduce corrosion of pipes by forming protective pipe scales. Orthophosphates can control lead, copper and iron corrosion through the formation of durable, low solubility scale, but are widely believed ineffective for sequestration or anti-scaling. Conversely, polyphosphates are effective sequestrants and anti-scalants, but can increase corrosion of plumbing materials. Here, we first critically reviewed the current state of the science, operational guidance, and knowledge gaps related to use of orthophosphate and polyphosphates for all three objectives. Three major gaps in understanding were identified and then addressed in subsequent chapters: 1) use of phosphates to achieve both sequestration and anti-scaling 2) mechanisms of iron sequestration, and 3) stabilization of magnesium silicate scale linings in a distribution system. In the critical review, we holistically conceptualize phosphate use as a three-dimensional (3-D) challenge of optimizing sequestration, anti-scaling and corrosion control. Despite nearly a century of widespread use, there is a poor scientific and practical understanding of how to use phosphates to achieve each of these key objectives, much less achieve synergies and avoid antagonistic effects. Many water systems are reliant on trial-and-error methods, or guidance from vendors of these proprietary chemicals, creating potential inefficiencies or even adverse unintended consequences. Effective sequestration of iron and manganese, to prevent formation of visible discoloration, can occur through four possible mechanisms which are undoubtedly dependent on the water chemistry (e.g., pH, hardness, redox). Anti-scaling of calcium carbonate occurs through threshold inhibition and crystal distortion, but sometimes phosphates can encourage scaling due to the precipitation of calcium phosphate. Corrosion control via orthophosphate is often effective, but polyphosphates can sometimes increase lead or copper levels in drinking water. Despite their widespread use in scientific studies, it was discovered that standardized measurements of color and turbidity do not fully account for the range of subjective consumer observations regarding cloudy or discolored water. At a constant apparent color of 110 Pt-Co, testing illustrated that relatively non-offensive air bubbles had a high turbidity of 74 NTU compared to just 0.1 NTU for offensively orange fulvic acid. Additionally, factors such as background color, type of light source, and direction of light significantly influenced perception of discolored water. For instance, under typical laboratory lighting conditions (light from above) with a white background, colors caused by iron, manganese, and fulvic acid were very prominent, whereas white calcium carbonate and magnesium silicate particles were more challenging to see. But white particles became much more prominent when the light source was from below or there was a darker background. A study of Fe sequestration was conducted to elucidate a mechanistic basis for the empirical trends revealed in the utility field study. As revealed in the literature review, polyphosphates could sequester Fe by inhibiting any step of the reaction sequence Fe2+ oxidation  precipitation of Fe(OH)3  particle agglomeration to visible sizes. Phosphates generally inhibited Fe2+ oxidation above about pH 7-8, dependent on chain length, and catalyzed oxidation at lower pHs. But in oxygenated waters above about pH 7, the dominant mechanism of sequestration was some combination of Fe3+ complexation and colloid stabilization at small particle sizes that were practically invisible. Increasing the phosphate chain length, phosphate concentration, and Si concentration caused more effective Fe sequestration, whereas Ca, Mg, and increased pH hindered its effectiveness. It was also discovered that orthophosphate can be an effective sequestrant under ideal conditions, polyphosphate can sequester more than 1 mg/L Fe despite some claims to the contrary, and Ca at very high doses can precipitate polyphosphates. During this dissertation work, a novel, thick (~1 mm), glassy magnesium silicate (MgSi) scale was discovered covering much of the pipe surfaces in a large water distribution system. This MgSi lining was hypothesized to be an extremely effective means of corrosion control that was important to maintain in its present state, as dissolution could cause it to detach from pipes, whereas further precipitation could clog them. To better understand how to maintain the scale, factors affecting the formation and dissolution of the MgSi solid were examined. Phosphate corrosion inhibitors had little effect on MgSi solubility at pH 8.5 and 10, while hexametaphosphate (HMP) and zinc orthophosphate slightly reduced Mg and Si dissolution rates at pH 7. Zinc orthophosphate reduced Mg dissolution by 50% and completely inhibited Si dissolution from the solid, while HMP decreased dissolution of Mg by 32% and Si by 63%. The magnesium silicate did not precipitate below pH 10 without the presence of a pre-existing seed solid. With a pre-existing seed scale, however, the MgSi further precipitated at a pH 8.5-9 in one source water and 7.5-8 in another. Below these pH levels, scale dissolution was shown to occur. Strategies were evaluated to help identify the equilibration pH for operation of a system with varying concentrations of silica, magnesium and pH. The two-dimensional (2-D) interplay of polyphosphate use for sequestration and anti-scaling was investigated for nine small utilities who rely on groundwater in North Carolina. Bench-top testing methods were developed to determine the 'optimal phosphate doses,' defined here as the lowest level of polyphosphate that maintains visually clear water and acceptable levels of scale formation. One proprietary polyphosphate chemical had an optimal sequestrant dose that depends on the concentration of Fe, Mn, Ca, and Mg. The dose (in mg/L as P) is equal to 58.5[Fe] + 59.7[Mn] + 0.041[Ca + Mg] + 0.4669 (units mM). Interestingly, color was well correlated with particulate (> 0.45 μm) Mn (R2 = 0.79) while turbidity was mostly correlated with particulate iron (R2 = 0.60). Furthermore, neither color nor turbidity measurements were reliable predictors of discoloration detected by eye. In the three utilities with higher hardness (> 100 mg/L as CaCO3), at least 3.6X more phosphate was needed for Fe and Mn sequestration than scale inhibition. But lab testing in very hard water with 300 mg/L as CaCO3 demonstrated that achieving anti-scaling, will sometimes require more polyphosphate than that needed for control of sequestration. Overall, this dissertation advances understanding of phosphate use in relation to important problems arising in water distribution or buildings. The innovative practical testing methods, improved practical understanding, and mechanistic insights can be applied to maximized the benefits of phosphates use while avoiding detriments. This is an important first step towards developing a rational holistic framework to guide utility decision-making regarding phosphate use. / Doctor of Philosophy / Phosphates are safe chemicals dosed to drinking water for a variety of objectives. Phosphates can prevent black water caused by manganese, red water caused by iron, clogging of pipes by precipitation of CaCO3, and to control corrosion of lead, copper and iron pipes. The simplest and least expensive phosphate is orthophosphate. Several orthophosphate molecules can be joined together to form a chain of 2 phosphates (pyrophosphate), a chain of 3 phosphates (tripolyphosphates), and chains up to 100s of phosphates in length. Some utilities only use orthophosphate to control pipe corrosion, and orthophosphate is not believed to be very effective for sequestration or anti-scaling. Conversely, polyphosphates can reduce red and black water from iron/manganese discoloration, and also inhibit the formation of calcium carbonate scale, but they sometimes increase corrosion of plumbing materials. Here, we review the current state of the science, operational guidance, and knowledge gaps related to use of ortho- and poly-phosphates. Three major gaps in understanding were identified and then addressed in subsequent chapters: 1) use of phosphates to achieve sequestration and anti-scaling simultaneously, 2) improve our understanding of how phosphates stop iron and red water (i.e., sequestration), and 3) stabilization of magnesium silicate scale linings in a distribution system. In a critical review, the use of phosphate for sequestration, anti-scaling and corrosion control was comprehensively examined. Despite nearly a century of widespread use, there is little understanding of how to properly use phosphates to achieve each objective. For dosing, many water systems rely on trial-and-error methods or guidance from chemical vendors, which could lead to mistakes that cause harmful unintended consequences. This could include elevated lead and copper release at the consumer's tap, increased consumer complaints caused by aesthetically displeasing water, increased head loss in pipes, and staining of dishes and appliances. Despite their widespread use in scientific literature, traditional measurements of color and turbidity are not always perfect measures of what is seen by eye. Additionally, factors such as background color, type of light source, and direction of light significantly influence the visual properties of water. For instance, under typical laboratory lighting conditions (light from above) with a white background, colors caused by iron, manganese, and fulvic acid were most noticeable, whereas white calcium carbonate and magnesium silicate particles were more challenging to see. In contrast, all particles became more observable when the light source was positioned below. A study of iron sequestration was conducted to investigate the ability of different phosphates to reduce the formation of red-colored water. As revealed in the literature review, polyphosphates could sequester iron in 3 different ways, but experiments revealed only two would be important in waters with higher pH and oxygen. Increasing the phosphate chain length, phosphate concentration, and silica concentration caused less visual discoloration, whereas calcium, magnesium, and increased pH had the opposite effect. It was also discovered that, at very high doses of calcium, a calcium-polyphosphate solid can precipitate. During this work, we also discovered a magnesium silicate (MgSi) scale covering much of the pipe surfaces in a large water distribution system. This MgSi lining is believed to protect underlying pipe materials from corrosion. To maintain the benefits of this protective scale, factors influencing its formation or dissolution were tested. The MgSi precipitated above pH 8.5-9 in one source water and 7.5-8 in another if a seed of the scale was present. Below this pH, the scale dissolved. The dosing of some phosphates slightly reduced the amount of scale which dissolved at a lower pH, but had no influence over the formation of more scale at higher pHs. Strategies were then evaluated to help the utility identify a good pH to operate the system, and to maintain the MgSi scale. The use of polyphosphate for sequestration and anti-scaling was investigated for nine small groundwater utilities in North Carolina. Laboratory experiments were conducted to determine the lowest level of polyphosphate that maintains visually clear water and acceptable levels of scale formation. This 'optimal polyphosphate dose' could be predicted by the iron, manganese, magnesium, and calcium concentrations of the water, at least for the utilities tested. Even in the three utilities with highest hardness in the study, more phosphate was needed for sequestration than inhibiting the formation of calcium carbonate scale. But lab testing in another very hard water with 300 mg/L as CaCO3, did demonstrate anti-scaling will sometimes require more polyphosphate than that required for sequestration. Overall, this dissertation advances understanding of phosphate use and abuse in relation to important problems arising in water distribution or buildings. The testing methods and improved practical understanding will help maximize the benefits of phosphates while avoiding detriments. This is an important first step towards developing a framework to guide utility decision-making regarding phosphate use for the benefit of consumers.