Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 83-95).

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Considerando que no Brasil o uso de diÃxido de cloro no tratamento de Ãgua à ainda pouco adotado em funÃÃo tanto de seu alto custo quanto da dificuldade de sua quantificaÃÃo, pretendemos comparar trÃs metodologias usadas para quantificar esse produto. Escolhemos a metodologia LGB (Lissamine Green B) e a comparamos com a metodologia EPA 327.0 ((Environmental Protection Agency) e a TitulaÃÃo AmperomÃtrica (referenciadas), ambas analisadas sob a mesma diluiÃÃo. Isso posto, visamos tambÃm comparar os efeitos da variaÃÃo da diluiÃÃo especificamente na metodologia TitulaÃÃo AmperomÃtrica. Para a metodologia de anÃlise, utilizamos o teste F, para analisar a precisÃo; o teste de ponto de HipÃtese, para analisar a exatidÃo entre as metodologias e a possÃvel existÃncia de tendÃncia entre elas; o teste T, para analisar a existÃncia de erros sistemÃticos entre as metodologias; o teste ANOVA one-way, para determinar os efeitos de diluiÃÃo na TitulaÃÃo AmperomÃtrica. A comparaÃÃo realizada nos permite concluir que a metodologia LGB nÃo apresentou variÃncia de repetibilidade e precisÃo intermediÃria pior que a apresentada na metodologia EPA 327.0 e na metodologia TitulaÃÃo AmperomÃtrica no nÃvel de confianÃa de 95%, apesar da dispersÃo em relaÃÃo à mÃdia e à mediana. / Considering that in Brazil the use of chlorine dioxide in water treatment is still not adopted due to both its high cost and difficulty of its quantification, we intend to compare three methods used to quantify this product. We chose the methodology LGB (not referenced) and compared with the EPA method 327.0 (Environmental Protection Agency () and amperometric titration (referenced), both analyzed under the same dilution. With that in mind, we aim to also compare the effects of varying the dilution specifically the methodology amperometric titration. for the analysis methodology, we use the F test to determine the accuracy, the test point hypothesis, to determine the accuracy of the methodologies and the possible existence of a tendency among them, the t test to analyze the existence of systematic errors among methods, the one-way ANOVA test to analyze the effects of dilution in the amperometric titration. The comparison allowed us to conclude that the methodology did not provide LGB variance of repeatability and intermediate precision worse than the one presented in the methodology EPA method 327.0 and the amperometric titration level of 95%, despite the dispersion from the mean and median.

The presence of pharmaceuticals in the environment has raised an emerging interest due to the fact that they pose negative environmental impact and health hazards related to long-term toxicity effects. As conventional treatments are not able to totally remove these substances it is necessary to seek for alternative advanced technologies such as oxidation with chlorine dioxide (ClO2). The objective of this master thesis is thus to find the most optimal dose – reaction time of ClO2 for the oxidation and maximum removal of selected environmentally relevant pharmaceuticals. Factorial design and subsequent optimization with MODDE was selected as the best approach to find the optimal dose – time. Batch oxidation tests were conducted on 100mL aliquots treated with ClO2 using wastewater effluent from Henriksdal WWTP. Thereafter solid phase extraction and final determination of pharmaceuticals was carried out on a high performance liquid chromatography- triple quadrupole mass spectrometry (HPLC-MS/MS). Results showed that applying a dose of 5 mg ClO2/L and a reaction time of 10 minutes, it is possible to remove more than a half of the 17 analyzed substances. Besides most of the pharmaceuticals with high and moderate environmental risk, would pose a low risk for the environment after treatment with the optimal ClO2 dose – reaction time. Despite the fact that ClO2 could successfully degrade most environmentally relevant pharmaceuticals, deeper research concerning the formation of toxic by-products after oxidative treatment needs to be done before upscaling this technology to pilot or full scale as a suitable end of pipe technology for pharmaceuticals removal.

This work aimed to determine how effective an SVP-LITE® chlorine dioxide plant at Vallviks Bruk was running. This was done by determining the chemical consumption per unit of chlorine dioxide produced. The calculations relied upon online instrumentation that was manually validated. The most important parameters were the conversion ratio of sodium chlorate into chlorine dioxide and the specific consumption of sodium chlorate, methanol, and sulphuric acid. The salt cake filter and dissolver were also examined to determine their impact. The total conversion ratio of sodium chlorate during a whole ECF (Elementally Chlorine Free) campaign were 93.12 %, somewhat lower than the target efficiency of 95.64 %. The specific chemical consumption was 1.695 kg sodium chlorate, 0.183 kg methanol, and 1.007 kg sulphuric acid per kg produced chlorine dioxide. The salt cake filter worked as intended to remove excess sulphuric acid, with the precipitate having the same sulphate and acidic content as the wanted form of sodium sesquisulphate Na3H(SO4)2. However, some sodium chlorate can get through, and the mean concentration in the dissolver was 1.3 g/dm3, equal to approximately 4 tons lost during a campaign. The filter may be more efficient in redissolving acidic species than chlorate salts. The reactor could theoretically be run more efficiently, but its production parameters is close to what is expected of such a plant. / Målet med det här arbetet var att undersöka effektiviteten av en SVP-LITE® klordioxidanläggning vid Vallviks Bruk. SVP-LITE® är en klordioxidproduktionslösning från EKA®. Det gjordes genom att undersöka konsumtionen av reagens per enhet producerad klordioxid. Beräkningarna gjordes från online-instrument som validerades manuellt. De viktigaste parametrarna var konverteringsgraden av natriumklorat till klordioxid samt den specifika förbrukningen av natriumklorat, metanol och svavelsyra. Sulfatlösaren undersöktes för att se hur saltkakefiltret fungerade och dess påverkan. Den totala konverteringsgraden av klorat till klordioxid under en hel ECF (Elementally Chlorine Free) kampanj var 93,12 %, något lägre än måleffektiviteten på 95,64 %. ECF är ett paraplybegrepp för att benämna blekning som inte använder klorgas men som kan använda andra kemikalier som innehåller klor, oftast klordioxid. Den specifika konsumtionen av reagens var 1,695 kg natriumklorat, 0,183 kg metanol och 1,007 kg svavelsyra per kg producerad klordioxid. Saltkakefiltret fungerade som tänk att ta bort överflödig svavelsyra och fällningen hade samma syrlighet som natriumseskvisulfat (Na3H(SO4)2. Natriumklorat kommer dock ut genom filtret och har i upplösaren medelkoncentrationen 1,3 g/dm3 vilket motsvarar en förlust på ca 4 ton under en kampanj. Det är möjligt att filtret är bättre att återupplösa syrliga specier än kloratsalter. Även om reaktorn teoretiskt kan köras mer effektivt är de nuvarande produktionsparametrarna nära de som kan förväntas av en sådan anläggning.

Three oxidants have been evaluated for use as alternative chemical pretreatments for Fena Lake, a surface water that supplies the U.S. Navy's Public Water System (PWS) on the volcanic island of Guam. The study consisted of two investigative components. The first and primary component included a bench-scale evaluation to study the effects of different pre-oxidant chemicals on the formation of chlorinated disinfection by-products (DBPs). The second and ancillary component included a series of water treatment and distribution system management studies that analyzed DBP formation within the treatment plant and water distribution system. The goal of this research was to reduce total trihalomethane (TTHM) and the five haloacetic acid (HAA5) formations in the PWS. In the primary component of the research, raw surface water from Fena Lake was collected by U.S. Navy personnel and shipped to University of Central Florida (UCF) laboratories for experimentation. Bench-scale tests that simulated the coagulation, flocculation, sedimentation and filtration (CSF) that comprises the Navy Water Treatment Plant (NWTP) were used to evaluate the use of two alternative pre-oxidants, potassium permanganate (KMnO4) and chlorine dioxide (ClO2) in lieu of gaseous chlorine (Cl2). The research assessed DBP formation by comparing several pretreatment scenarios, namely: (1) no pretreatment, (2) chlorine pretreatment, and (3) alternative oxidant pretreatment. KMnO4 pretreatment resulted in the lowest percent reduction of TTHMs and HAA5 relative to chlorine pretreatment, at 5.7% and 22.7%, respectively; however, this amount was still a reduction from the results demonstrated for the chlorine pretreatment condition. Without using a pre-oxidant, TTHM and HAA5 formation were reduced by 22.8% and 37.3%, respectively, relative to chlorine pretreatment. Chlorine dioxide demonstrated the greatest TTHM and HAA5 reduction relative to chlorine pretreatment at 34.4% and 53.3%, respectively. The second component of research consisted of a series of studies that evaluated distribution system operations and management alternatives to identify opportunities that could achieve DBP reduction within the PWS. Three concerns that were addressed were the NWTP's compliance with the U.S. Environmental Protection Agency's (USEPA's) Stage 2 Disinfectants/Disinfection By-Products (D/DBP) Rule, variable hydraulic detention times within a small subdivision in the distribution system, and severe weather. It was determined that: (1) A decision based on in-plant studies to cease prechlorination at the NWTP resulted in a decrease in TTHMs and HAA5s throughout the distribution system by 62% and 75%, respectively; (2) A fluoride tracer study led to the discovery of a valved pipeline responsible for elevated DBPs because of excessive water age that when exercised and managed resolved intermittent DBP spikes in the PWS; and (3) when the NWTP's ballasted floc clarifier (BFC) was operated in-series prior to the conventional CSF process during severe weather conditions the TTHM and HAA5 were below 39 ug/L and 29 ug/L, respectively, proving BFC in-series is a practical option for the plant during severe weather.

This study focused on evaluating the antimicrobial activity of chlorine dioxide (ClO2) and different plant-based antimicrobials (carvacrol, thymol, and eugenol as bioactive compounds and muscadine extract- ME and blueberry extract- BBE as plant extracts) against selected foodborne pathogens under in vitro conditions and on produce (spinach and blueberries). In addition, bacterial microbiota associated with blueberries and blueberry farm environments from three different regions: Cundinamarca, Colombia; Mississippi, United States; and Guadalajara, Mexico, was determined. Under in vitro conditions, carvacrol and thymol were more effective (lower MICs and MBCs) than eugenol against Salmonella spp., Escherichia coli O157:H7 (MIC=MBC=0.2 mg/ml), and Listeria monocytogenes (MIC=MBC=0.4 mg/ml). Both plant extracts had the same MIC and MBC for Salmonella spp. while BBE had stronger bactericidal effect on Escherichia coli O157:H7 (MBC=150 mg/ml) and ME on L. monocytogenes (MBC=100 mg/ml). ClO2 had stronger bacteriostatic effect on L. monocytogenes (MIC=1 ppm) than on the Gram-negative bacteria (MIC=3 ppm). For the produce study, 300 mg/ml ME exerted the highest (P ≤ 0.05) E. coli O157:H7 reduction (4.5 log CFU/g at day 1) on spinach, and 3 ppm ClO2 + 300 mg/ml ME had the highest (P ≤ 0.05) L. monocytogenes reduction on both (4.5-5.6 log CFU/g). There was a similar (P>0.05) E. coli O157:H7 reduction on blueberries, regardless of antimicrobial treatment. For the microbiota study, Proteobacteria was the most abundant phylum in blueberries, soil, and water, with the exception of fruits from Mexico. Blueberries grown on the different regions shared two predominant genera: Heliorestis (10.5-47.4%) and Thiomonas (5.0-9.1%). Nonetheless, alpha and beta diversity revealed that blueberry microbiota structures were distinctive. PCoA plots revealed that within regions the microbial composition distribution was different (P ≤0.05) among fruits, soil, and water. Based on the results, ME combined with ClO2, could represent an antimicrobial alternative against foodborne pathogens for the produce industry. Furthermore, the study of the microbiota provided a good understanding on the bacterial community profile in blueberries and the blueberry farming environment across regions.

Chemical disinfection is the cornerstone of safe drinking water. However, the use of chemical disinfection results in the unintentional formation of disinfection by-products (DBPs), an outcome of reactions between the disinfectant and natural organic matter (NOM) present in the native (raw) water. DBPs are suspected carcinogens, and as such, have been regulated by the U.S. Environmental Protection Agency (USEPA) under the Safe Drinking Water Act (SDWA). This document reports the results of a study that investigated the use of chlorine dioxide pre-oxidation for the reduction of DBP precursors, and subsequently, DBP formation potential (FP). To determine the effectiveness of the chlorine dioxide pre-oxidation process, two surface waters were studied: raw water from Lake Claire (Orlando, FL) and raw water from the East Maui Watershed (Makawao, HI). Lake Claire water contains approximately 11-12 mg/L of NOM and 35 mg/L as CaCO3 of alkalinity, while the Maui source water typically ranges between 7-8 mg/L of NOM with 2-10 mg/L as CaCO3 of alkalinity. Two chlorine dioxide doses were investigated (0.75 mg/L and 1.5 mg/L) and compared to a control to quantify the effectiveness of this advanced pre-treatment oxidation process. Water collected at each site was subject to the following treatment process: oxidation, coagulation, flocculation, sedimentation, ultrafiltration, and disinfection with free chlorine. Disinfection by-product formation potential (DBPFP) analysis showed that ClO2 pre-oxidation, in general, increased the 7-day DBPFP of the East Maui water, and decreased the 7-day DBPFP of the Lake Claire source water. For the Lake Claire water at the higher ClO2 dose, total trihalomethanes (TTHM) were decreased by 37 percent and the five regulated haloacetic acids (HAA5) by 23 percent. For the East Maui source water at the higher ClO2 dose, TTHM’s were increased by 53 percent and HAA5’s by 60 percent. Future research should determine the effect of alkalinity on DBPFP, which could be the reason why chlorine dioxide pre-oxidation caused one water source’s DBPFP to decrease and the other to increase.

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