Browsing by Subject "Natural organic matter"
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Item Defluoridation and natural organic matter removal in drinking waters by alum coagulation(2014-05) Stehouwer, Mark Lawrence; Lawler, Desmond F.; Katz, Lynn E.Fluoride naturally occurs in some ground and surface waters at high concentrations all around the world. Due to increasing health concerns about over-exposure to fluoride in drinking water, the United States Environmental Protection Agency (USEPA) has begun to review fluoride as a drinking water contaminant. Should the USEPA decide to lower the fluoride maximum contaminant limit (MCL), many water systems in addition to those already struggling to meet the fluoride MCL will require defluoridation as part of their drinking water treatment process. Alum coagulation was investigated as a defluoridation treatment strategy in this research project. Surface and blended (ground/surface) drinking water sources with high fluoride concentrations pose a unique challenge to defluoridation by alum coagulation because of the presence of both natural organic matter (NOM) and fluoride. Defluoridation of synthetic and natural waters using jar tests elucidated interactions of fluoride, NOM, and aluminum during alum coagulation. Alum coagulation was able to remove 80% of fluoride from natural waters with a 500 mg/L alum dose; however, 50% fluoride removal was observed to be possible with an alum dose of 150-170 mg/L. The optimum pH for fluoride removal in synthetic and natural waters was observed to be approximately 6.5 and was found to be an important factor in determining the overall performance of alum coagulation. The presence of fluoride during alum coagulation was found to reduce the removal of three low molecular weight (LMW) organics, acting as surrogates for NOM, to different extents depending on their functionality. The presence of LMW organic acids in synthetic waters did not impact the removal of fluoride; however, increasing NOM concentrations in the natural waters likely accounted for decreasing fluoride removals observed in the natural waters. Additional jar tests with natural waters revealed that pH adjustment was unnecessary for defluoridation of high pH and high alkalinity waters and that an enhanced precipitation effect occurred at low alum doses when no pH adjustment was made during alum coagulation. The enhanced precipitation effect caused comparable or enhanced removals of fluoride and NOM to be observed despite system pH values being higher than the optimal defluoridation pH of 6.5. Lower aluminum residuals were also observed as part of the enhanced precipitation effect, suggesting that when precipitation begins under high pH conditions, fluoride interference does not occur and therefore promotes more precipitate formation with greater available surface area for adsorption. However, as precipitation occurs, pH drops, and fluoride increasingly interacts with the aluminum precipitate resulting in greater overall fluoride removals.Item Drinking water treatment by alum coagulation : competition among fluoride, natural organic matter, and aluminum(2012-12) Alfredo, Katherine Ann; Lawler, Desmond F.; Katz, Lynn Ellen; Liljestrand, Howard M.; Holcombe, James A.Some community water systems using sources containing elevated levels of fluoride, in the United States and worldwide, struggle to treat their drinking water to healthy fluoride concentrations. Many treatment plants in the U.S. currently use aluminum based salts, such as aluminum sulfate and polyaluminium chloride, as coagulants during conventional treatment for removal of particles from drinking water sources. Moreover, enhanced aluminum sulfate, or alum, coagulation requires higher concentrations of aluminum added to the process and has been shown to be effective for removal of disinfectant byproduct precursors, i.e., natural organic matter (NOM). The presence of fluoride may interfere with the formation of aluminum hydroxide precipitates, and interrelationships among NOM, aluminum precipitation and fluoride removal are not well understood. A fundamental understanding of how fluoride alters the properties of aluminum precipitates and how fluoride and NOM molecules compete as ligands interacting with soluble aluminum species is lacking. As a result, the development of guidelines for implementation and optimization of a treatment scheme that uses aluminum in the presence of fluoride requires a multi-faceted approach in which the development of a mechanistic understanding of these interactions is conducted in concert with macroscopic experiments to identify optimum conditions for simultaneous removal of fluoride and NOM. To date, little research has looked at the efficiency of removing both fluoride and organics from the perspective of the precipitation process. To provide a foundation for revising treatment techniques, this research evaluated the effect of co-precipitating aluminum in the presence of fluoride, organics, and in multi-ligand systems to characterize the solid precipitate and removal competition. This research verified the formation of a co-precipitate in the presence of fluoride and certain low molecular weight organics. Co-precipitation from organics and fluoride competes for removal, especially at low alum coagulant doses, complicating treatment for resource limited areas.Item Fluoride, natural organic matter, and particles : the effect of ligand competition on the size distribution of aluminum precipitates in flocculation(2016-05) Herrboldt, Jonathan Philip; Lawler, Desmond F.; Katz, Lynn EllenFluoride occurs at elevated concentrations naturally in surface and ground waters around the world. If consumed at low concentrations in drinking water (< 1.5 mg/L), fluoride is shown to reduce the occurrence of dental caries and the Centers for Disease Control and Prevention named fluoridation of public water systems one of the 10 Great Public Health Achievements of the 20th Century (CDC, 1999). However, prolonged exposure to high concentrations of fluoride (> 2.0 mg/L) causes adverse health effects to teeth and bones. For this reason the United State Environmental Protection Agency (USEPA) enacted a maximum contaminant level (MCL) for fluoride at 4.0 mg/L. This rule is currently under review following a recent risk assessment and may be lowered. If the MCL were lowered, water systems previously meeting treatment standards would suddenly find themselves out of compliance and will need to implement additional treatment to meet the new standard. Defluoridation by alum coagulation is a proposed defluoridation method. However, the interaction between fluoride and natural organic matter (NOM) and their effects on the particle size distribution of aluminum precipitates is not well understood. Because the particle size distribution of aluminum precipitates is an important parameter in the efficiency of sedimentation and filtration systems, a thorough understanding of these interactions and their potential effect on sedimentation and filtration is needed to inform the implementation of defluoridation by alum coagulation. This work utilized a series of jar tests on synthetic surface water to determine the effect of fluoride and NOM on the particle size distribution of aluminum precipitates. It was found that fluoride caused the volume distribution of aluminum precipitates to shift toward smaller particle sizes. However, NOM caused the formation of a larger number of aluminum precipitates, which resulted in a dramatic increase in the total volume of precipitates. When both fluoride and NOM were in the system, a combination of the two effects was observed: the volume distribution shifted toward smaller particle sizes but the peak of the distribution shifted toward a greater volume, indicating both smaller particles were being formed and a greater overall volume of particles precipitated.Item Impact of bromide, NOM, and prechlorination on haloamine formation, speciation, and decay during chloramination(2009-12) Alsulaili, Abdalrahman D.; Speitel, Gerald E.; Katz, Lynn EllenThe Chlorine-Ammonia Process was developed recently as a preoxidation process to minimize the formation of bromate during ozonation of the waters containing a significant bromide concentration. Chlorine is added first, followed by ammonia 5-10 minutes later, with the goal of sequestering bromide in monobromamine before the subsequent ozonation step. The goal of this research was to improve the Chlorine-Ammonia Process by introducing a very short prechlorination step (i.e., 30 seconds before addition of ammonia) to minimize overall disinfection by-product formation. Also, in this strategy, formation of a powerful halogenating agent, HOBr, is minimized and bromochloramine (NHBrCl) is used predominantly instead of monobromamine to sequester bromide during ozonation. To support this improved approach to bromide sequestration, this study examined the formation and decay of bromochloramine as a function of operating conditions, such as pH and Cl2/N ratio, and refined a chemical kinetic model to predict haloamine concentrations over time. Two natural organic matter (NOM) sources were used in this study (Lake Austin, Texas and Claremore Lake, Oklahoma) to study the effect of NOM on monochloramine and total chlorine decay after 30 seconds of prechlorination. The rate of the reaction between haloamines and fast and slow sites on the NOM was estimated. A kinetics model was developed to model total chlorine decay after a short prechlorination time. The model is based on the Unified Haloamine Kinetic Model developed by Pope (2006). Pope`s model failed to model the initial monochloramine concentration after 30 seconds prechlorination time as well as the monochloramine and total chlorine decay over time. The modified model shows an excellent prediction of monochloramine and total chlorine decay after 30 seconds prechlorination time at pH range of 6.5-8.0 and over a carbonate buffer concentration range of 2-10 mM. The model includes a new bromochloramine decay scheme via the reaction with monochloramine and with itself. In addition, new rate constants for the reaction of HOCl with bromide ion and reaction of HOBr with monochloramine were added. The hypobromous acid formation rate was found to be an acid-catalyzed reaction, which confirms the finding of Kumar et al. (1987). A new value of the acid catalysis effect of hydrogen ion was estimated. New terms were introduced to the hyprobromous acid formation rate including the acid catalysis effect of bicarbonate, carbonic acid, and ammonium ion. In addition, the reaction of HOBr with monochloramine to form bromochloramine was found to be an acid-catalyzed reaction, and a new value of the rate constant was estimated.Item Kinetics of ciprofloxacin degradation by ozonation : effects of natural organic matter, the carbonate system, and pH(2010-08) Marron, Corin Ann; Katz, Lynn EllenThe presence of pharmacologically active and persistent compounds in drinking water sources is an environmental and public health concern. Sources of pharmaceuticals in the aquatic environment include wastewater treatment plant effluents and veterinary use. Antibiotics are of special concern because of their role in the spread of bacterial resistance. Conventional drinking water treatment processes are often ineffective for removing trace organic contaminants. Ozonation processes have demonstrated the ability to remove pharmaceutical compounds from drinking water supplies. During the ozonation of drinking water, the primary oxidants are ozone and hydroxyl radicals formed during the decomposition of ozone. Both oxidants contribute to the removal of pharmaceutical compounds; however, the relative rates of destruction by these two oxidants depends on the treatment operating conditions, the background water chemistry and the structure and reactivity of the target compound. This study investigated the relative impact of natural water characteristics, such as pH, the carbonate system, and natural organic matter, on the removal of the fluoroquinolone antibiotic ciprofloxacin by ozonation processes. Rate constants for k"O3, Cip obtained at pH 7 were approximately one order of magnitude higher than at pH 5 because ciprofloxacin changes from a positively charged cation to a neutral species over this pH range. The results showed that there was very little variation of the rate constants for ciprofloxacin oxidation by O₃ or hydroxyl radicals regardless of the carbonate concentration or the presence of the two organic matters studied in this research. Typical values for k"O3, Cip and k"HO°, Cip obtained at pH 7 ranged between 1.49x10⁴ and 1.64x10⁴ M⁻¹s⁻¹ and 1.29x10¹⁰ to 1.80x10¹⁰ M⁻¹s⁻¹, respectively. However, the presence of carbonate and other hydroxyl radical scavengers did have an impact on O₃ and hydroxyl radical exposure. The relative impact of these two oxidants changed depending on the pH of the system and the presence of carbonate and natural organic matter.Item Natural Organic Matter (NOM) in Aquatic Systems: Interactions with Radionuclides (234Th (IV), 129 I) and Biofilms(2011-10-21) Zhang, SaijinA series of laboratory and field investigations were carried out to elucidate the importance of natural organic matter in aquatic systems, i.e., trace element scavenging (e.g., 234Th) by exopolymeric substances (EPS), formation of biofilms, as well as interactions with 129I. A method involving cross flow ultrafiltration, followed by a three-step cartridge soaking and stirred-cell diafiltration, was developed for isolating EPS from phytoplankton cultures, especially in seawater media. EPS isolated from a marine diatom, Amphora sp. was then subjected to semi-quantitative (e.g., carbohydrate, proteins) and quantitative analysis (e.g., neutral sugars, acidic sugars, sulfate). It appeared that Th (IV) binding by EPS was dominated by the acidic polysaccharides of fraction. For EPS of biofilms collected from polluted streams, hydrophobic proteins were the most abundant components in EPS, followed by more hydrophilic carbohydrates. However, chemical composition of carbohydrates or proteins, i.e., monosaccharides and amino acids, respectively, varied with environmental conditions and substrata applied, which suggests that the formation of biofilms on different substrates is regulated by specific properties of microorganisms, environmental conditions and nature of substratum. No correlation between relative hydrophobicity of substratum and development of biofilm was found in this study. A sensitive and rapid GC-MS method was developed to enable the determination of isotopic ratios (129I/127I) of speciated iodine in natural waters. At the F-area of the Savannah River Site (SRS), iodine species in the groundwater consisted of 48.8 percent iodide, 27.3 percent iodate and 23.9 percent organo-iodine. Each of these iodine species exhibited vastly different transport behavior in the column experiments using surface soil from the SRS. Results demonstrated that mobility of iodine species depended greatly on the iodine concentration, mostly due to the limited sorptive capacity for anions of the soil. EPS, especially enzymes (e.g., haloperoxidases) could facilitate the incorporation of iodide to natural organic carbon. At high input concentrations of iodate (78.7 ?M), iodate was found to be completely reduced and subsequently followed the transport behavior of iodide. The marked reduction of iodate was probably associated with natural organic carbon and facilitated by bacteria, besides inorganic reductants (e.g., Fe2 ) in sediments and pore water.Item Oxidation of pharmaceuticals : impacts of natural organic matter and elimination of residual pharmacological activity(2011-08) Blaney, Lee Michael; Lawler, Desmond F.; Katz, Lynn Ellen; Liljestrand, Howard M.; Richburg, John H.; Speitel Jr., Gerald E.; Kirisits, Mary JoAnthropogenically-derived substances, including pharmaceuticals and personal care products, endocrine-disrupting chemicals, and pesticides, are increasingly being detected in drinking water supplies and wastewater effluents. Concerns over the presence of these compounds in water supplies include their ability to impart toxicological activity, their capacity to spread antibiotic resistance, and their potential to affect cell-signaling processes. For these reasons, water treatment processes geared towards removal of these trace organic contaminants are vital. In this work, ozone was used to treat four pharmaceutical contaminants: ciprofloxacin, cyclophosphamide, erythromycin, and ifosfamide. Ciprofloxacin and erythromycin are antibiotic/antimicrobial compounds, and cyclophosphamide and ifosfamide are chemotherapy agents. Ozone effectively transformed all four pharmaceuticals, even in the presence of background natural organic matter, which exerts a considerable ozone demand. The apparent rate constants for the reaction of the pharmaceuticals with ozone at pH 7 were determined: 3.03 M-1s-1 for cyclophosphamide; 7.38 M-1s-1 for ifosfamide; 1.57×104 M-1s-1 for ciprofloxacin; and 7.18×104 M-1s-1 for erythromycin. Cyclophosphamide and ifosfamide, which do not react quickly with ozone, exhibited high rate constants (2.7×109 M-1s-1) for transformation by hydroxyl radicals, which are formed through ozone decomposition. Nevertheless, complete removal of cyclophosphamide and ifosfamide was achievable using a novel continuous aqueous ozone addition reactor and an ozone-based advanced oxidation process (peroxone). In ozone-based processes, pharmaceuticals are systematically transformed via complex oxidative pathways towards CO2, H2O, and the oxidized forms of other elements. Intermediate oxidation products containing oxygen atoms or hydroxyl groups substituted into the chemical structure of the parent pharmaceutical were identified using liquid chromatography-mass spectrometry (LC-MS). Given the structural similarity of intermediate oxidation products to the parent pharmaceuticals, an antimicrobial activity assay was employed to monitor the removal of pharmacological activity associated with ciprofloxacin, erythromycin, and their respective intermediate oxidation products throughout treatment. For solutions containing ciprofloxacin or erythromycin, ozone was able to completely eliminate the corresponding antimicrobial activity. Ciprofloxacin intermediate oxidation products were pharmacologically active; however, erythromycin’s intermediate products did not contribute to the residual antimicrobial activity. These results suggest that the design of conventional and advanced ozone-based processes must incorporate ozone demand from background organic matter and account for destruction of pharmacologically active intermediates.