While free (breakpoint) chlorination is widely utilized in humanitarian water treatment, a main challenge limiting its effective application is in determining the initial dose to satisfy both health requirements and aesthetic considerations (i.e. taste and odour). International guidelines and studies showed varying recommendations for the initial chlorine dose and many did not consider chlorine decay during water transportation and storage for up to 24 hours. The main objective of this thesis is to develop a tool for humanitarian staff to accurately determine the initial chlorine dose for achieving free chlorine residual (FCR) objectives with the limited instrumentation and information in the field. The first manuscript included in the thesis gathered and evaluated seven basic chlorine decay models’ applicability in humanitarian treatment contexts. All seven models were found able to accurately describe chlorine decay in water representative of humanitarian treatment contexts with more than half of the regression resulted in R2 over 0.95. However, each model had its own limitations, which were discussed. The second manuscript involved conducting extensive chlorine decay tests in water with different characteristics, explored the relationships between the estimated chlorine decay constant and several water parameters including pH, turbidity, ultraviolet absorption at 254 nm wavelength (UVA254), temperature and 30-minute chlorine demand. It was found that the UVA254 of water followed linear and exponential relationships with the decay constant in Feben and Taras’s empirical model and that in the first order model respectively. Arrhenius-type relations were verified between the decay constant and water’s temperature. A model developed to predict FCR decay in water with known 30-minute chlorine demand accurately predicted FCR level in synthetic water (with humic acid being the main constituent) but underpredicted FCR decay in water with additional chlorine consuming matter. Further research on additional chlorine decay mechanisms are needed to expand the applicability of the model. / Graduate / 2021-04-13

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.

Bibliography: pages 112-138. / The large volume of seawater used for cooling at Koeberg Nuclear Power Station contains many planktonic organisms which are exposed to heat, chlorine and physical stress during their passage through the system. Phytoplankton biomass, measured as chlorophyll a, was reduced by an average of 55.32% due to entrainment, and productivity was decreased by 38.30% on average, mainly due to chlorination. Zooplankton mortality averaged 22.34% for all species and 30.52% for copepods, the dominant group. The copepod Paracartia africana was used in laboratory experiments designed to simulate entrainment. Latent mortality was monitored up to 60 hours after a 30-minute application of stress factors (physical stress was not simulated), and approximately 75% of the total mortality occurred within the 30-minute period. Male Paracartia experienced higher mortalities than females. Extrapolation of these results predicts an overall entrainment mortality (including latent mortality) of 40% for copepods and 29.04% for total zooplankton, although the latter cannot be substantiated. Plankton entrainment at Koeberg was not considered to be overly detrimental to the marine environment because of the very localised area affected, rapid dispersion of heat and chlorine, rapid regeneration times of phytoplankton and some zooplankton, low abundance of commercially important species and potential recruitment from the surrounding productive Benguela upwelling region.

The physicochemical properties and chemical reactivity of dissolved organic matter (DOM) are of tremendous practical significance in both natural and engineered aquatic and terrestrial systems. DOM is frequently extracted, fractionated, and concentrated from environmental samples using a variety of operationally defined physical and chemical processes in order to facilitate study of specific physicochemical properties and aspects of its chemical reactivity. This study was conducted to systematically examine the influence of operationally defined physical and chemical characterization methods on observed DOM physicochemical properties and reactivity with aqueous chlorine. The effects of chemical separation were evaluated by applying an existing resin adsorption based procedure which simultaneously extracts and fractionates DOM and inorganic constituents into hydrophobic and hydrophilic acid, base, and neutral dissolved material matrix (DMM) fractions. Physical separation based on DOM apparent molecular weight (AMW) was also evaluated using batch ultrafiltration (UF) data in conjunction with a suitable membrane permeation model. Linear independence of membrane solute transport was theoretically described using non-equilibrium thermodynamics and experimentally demonstrated for AMICON® YC/YM series UF membranes. Mass balances on DMM fraction constituents in untreated and previously coagulated natural waters indicated that quantitative recovery (100 ± 2%) of DOM constituents was achieved, while recovery of inorganic constituents such as iron and aluminum was substantially incomplete (30%-74%). Comparison of whole-water DOM properties with those mathematically reconstituted from DMM fractions demonstrated a marked shift in DOM properties toward lower AMW. Evidence of pH induced partial hydrolysis of protein, polysaccharide, and ester DOM components was also observed. Decreased specific Cl2 demand (mmol DCl2/ mmol DOM) and specific trihalomethane formation (mmol THM/mmol DOM) following chemical fractionation were attributed to increased molar DOM concentration and decreased DOM association with colloidal iron oxide surfaces. Collectively, the results of this research indicate that operational characterization methods result in alteration of DOM physicochemical properties and reactivity with aqueous chlorine, and caution is therefore advisable when interpreting the results of studies conducted using chemically extracted or fractionated DOM. / Ph. D.

The mining industry is a significant contributor to the Canadian economy. However, the mining activities can be detrimental to the environment due to the release of pollutants. Ammonia is one of the noxious and toxic contaminants associated with mining, ammonia contamination is created by the oxidizing agent in explosives. The explosives impacted mining wastewater (EIMWW) usually contains ammonia and other metal ions. The ammonia in EIMWW could harm the aquatic environment by the depletion of oxygen and its lethal toxicity to aquatic organisms. Before release to environment, EIMWW needs to be treated with an easy-to-operate method for ammonia removal at the remote mining sites. Ion-exchange (IE) with zeolite is an effective method for ammonia removal that is easy-to-operate, is not significantly impacted by cold temperature or toxicity effects. However, the traditional IE regeneration approach of using high concentration NaCl solutions creates a secondary polluting stream. Chlorine regeneration of ammonia-loaded zeolite appears to be a promising option, an evaluation of this option is the main topic of this thesis. This thesis includes three initiatives. The first is a set of multi-cycle batch loading-regeneration tests to assess the viability of ammonia removal with a commercial zeolite (SIR-600) for the treatment of a synthetic EIMWW (containing total ammonia nitrogen (TAN), K, and Ca) and to examine the performance of different ion-exchange regeneration solutions. The long-term TAN uptake of SIR-600 regenerated using a NaOCl (100 mg free Cl2/L) solution was 0.24 meq/g, which was approximately 20% lower than that after a NaCl regeneration. However, chlorine regeneration is promising because the selectivity of SIR-600 for TAN over Ca and K increased after the chlorine regeneration. To simulate recycling of the NaOCl regenerants, K and Ca were added to the NaOCl solution, it did not substantially affect the subsequent SIR-600’s ion uptake. This initiative represents a significant contribution since the earlier studies into chlorine regeneration did not investigate the impact of competing ions. The second initiative addressed concerns regarding the long-term integrity of SIR-600 arising from its exposure to high chlorine concentrations during the regeneration. The five-week long chlorine batch exposure tests with solutions of up to 1000 mg free Cl2/L showed that chlorine exposure did not significantly affect the SIR-600’s characteristics in terms of particle size distribution, surface area, FTIR spectra and ion uptake. Thus, SIR-600 has the potential for long-term use in field applications. The final initiative evaluated the feasibility of chlorine regeneration for continuous flow IE column systems used for ammonia removal from a synthetic EIMWW. Continuous flow column systems are important because these are the standard IE units used in full-scale applications. Multi-cycle column loading-regeneration tests were performed to compare the zeolite performance using a NaOCl (1000 ppm as free Cl2) solution with that using a 5% NaCl regeneration. The influence of loading duration was also assessed. The use of 6-hr loading cycles were shown to be preferable to 23-hr loading cycles because it had lower effluent concentrations and they could achieve higher overall TAN mass removals per unit time. After three operational cycles, the SIR-600 had similar TAN uptake performances (0.21 meq/g Vs. 0.21 meq/g) after NaOCl regeneration and after salt (NaCl) regeneration. This is in contrast to the lower TAN uptakes for the NaOCl regeneration in the batch tests, this indicates that batch tests are not always representative of full-scale applications. Compared to NaCl regenerated SIR-600, SIR-600 after NaOCl regeneration had a higher preference for TAN over Ca and K, which makes this type of regeneration very promising. Its only apparent limitation is that the NaOCl regeneration required a longer duration. During the NaOCl regeneration, the main mechanism appears to be the oxidation of ammonia to nitrogen gas and hydrogen ions, however the Na in the NaOCl solution also seems to have a role in the regeneration.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19687号 / 工博第4142号 / 新制||工||1639(附属図書館) / 32723 / 京都大学大学院工学研究科航空宇宙工学専攻 / (主査)教授 斧 髙一, 教授 稲室 隆二, 教授 青木 一生 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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.

USEPA regulations of Disinfection By-Products (DBPs) require water suppliers to be in compliance with maximum contaminant levels set by the agency’s Stage 2 DBP Rule. Controlling watershed sources of byproduct precursors are of interest to water suppliers. By-product formation potential and DOC (dissolved organic carbon) character were evaluated at eight sites on four dates (n=32). All sites are within Springfield Water and Sewer Commission’s Cobble Mountain Reservoir watershed (Blandford and Granville, Ma). The goal was to investigate how DBPFP (DBP formation potential) changes in relation to landscape driven changes in DOC chemical characteristics. Analysis was performed on raw water samples using UV-Visible Spectroscopy. 1H Nuclear Magnetic Resonance Spectroscopy (NMR), and Fourier Transform Infrared Spectroscopy (FT-IR) were performed on solid phase extractable (SPE-C18) hydrophobic DOC. Changes in DBPFP are related to landscape changes in hydrophobic DOC characteristics. On three of the four sample dates (n=24) DBPFP was positively correlated to the E2:E3 ratio (R2=.37), SUVA (R2=.72), percent aromatic resonance (R2=.60), and percent carbohydrate resonance (R2=.44). DBPFP on three sample dates (n=24) was negatively correlated to percent aliphatic resonance (R2=.48). DOC aromaticity, SUVA and specific formation potential were lowest in headwater streams and increased with distance downstream. Substantial reductions in DOC concentration are seen upon reservoir export. For most parameters headwater in-stream variability was greater than inter-stream variability. Differences among headwater streams of different forest type are not distinguishable in our small sample size (n=12). Only slight differences in specific formation potential were observed among two different depth samples in Cobble Mountain Reservoir. Our results have implications for watershed management practices in the drinking water supply industry of New England.

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