Chemical modification of cellulose has been of growing interest, owing to the abundance and processing challenges of natural cellulose. To date, etherification and esterification are the most effective strategies to modify physicochemical properties of cellulose and append new functionalities. However, they typically require relatively harsh conditions, thus limiting introduction of new functional groups. An alternative strategy to synthesize novel cellulose derivatives is to append a good leaving group to cellulose backbone, followed by nucleophilic substitution reaction. Though tosylation and bromination of cellulose are frequently used, they have drawbacks such as chemo- and regioselectivity issues, high cost, and difficulty in purification. We have successfully developed a method to chemo- and regioselectively chlorinate cellulose esters using MsCl. Compared to bromination of cellulose typically used, this chlorination method has many advantages, including low cost of reagents and ease of separation. The chlorinated cellulose esters are useful intermediates for appending new functionalities by displacement reactions. We have synthesized a library of cellulose ester derivatives by this chlorination/nucleophilic substitution strategy, including cationic and anionic cellulose ester derivatives. These cellulose ester derivatives possess great potentialiii for various applications, including amorphous solid dispersion, tight junction opening, anionic drug delivery, and gas separation membranes. / MS

High arsenic concentrations (>100 ppb) have been measured in wells completed in the Ordovician St. Peter sandstone aquifer of eastern Wisconsin. The primary source of arsenic is As-bearing sulfide minerals within the aquifer. There is concern that periodic disinfection of wells by chlorination may facilitate arsenic release to groundwater by increasing the rate of sulfide mineral oxidation. Current guidance from the Wisconsin Department of Natural Resources recommends a "low-dose" treatment of 20% of the chlorine strength and 10% of the of the contact time of chlorine treatments used in non-arsenic impacted wells for well disinfection and biofilm removal. In order to provide information pertaining to WDNR's recommendations, St. Peter sulfide minerals were reacted with a range of chlorine "shock-treatments" similar to those occurring in wells. This study focuses on abiotic processes that mobilize arsenic from the solid phase during controlled exposure to chlorinated solutions. Thin sections were made from aquifer material collected at Leonard's Michael quarry, located in Winnebago County, Wisconsin. Bulk arsenic content of this material was measured as 674 ppm. Quantitative EPMA analysis shows As zoning in pyrite grains with concentrations up to 1 wt. % As. After mineral characterization, the thin sections were exposed to solutions of 60 mg/L "free chlorine," 1200 mg/L "free chlorine," and nanopure water (control) at pH 7.0 and pH 8.5 for 24 hours. Thin sections were then analyzed to measure changes in the pyrite surfaces. For solution experiments, aquifer material was crushed to between 250 μm and 355 μm mesh sizes (S.A. ~ 50 cm2/g – 60 cm2/g, Foust et al. 1980) and reacted under the same conditions as the thin sections in a batch reactor. Solution samples were collected periodically during the 24 hour exposure and analyzed for arsenic, iron, and sulfate ion. Pyrite oxidation is shown to dramatically increase with increasing chlorine concentrations as shown by measurements of released sulfate ion, used here as the reaction progress variable. EPMA maps also reveal complete oxidation of pyrite cements to Fe-oxyhydroxides at 1200 mg/L "free chlorine" and pH 7.0. This behavior does not occur at lower concentrations or higher pH. Arsenic release to solution does not appear to be directly correlated to increasing chlorine concentrations, but is governed by Fe-oxyhydroxide nucleation, which inhibits the release of dissolved arsenic at higher concentrations of chlorine. / Master of Science

Carbamazepine (CBZ) is an antiepileptic drug widely detected in drinking water supplies and wastewater effluent. It has been previously found that CBZ is recalcitrant to biological removal processes. Therefore, active CBZ will be exposed to wastewater effluent disinfection processes, which for most treatment plants in the United States involves the addition of free chlorine. However, the chlorination mechanisms of CBZ have not been fully investigated and are currently poorly understood. Our experimental studies were conducted to examine the chlorination of CBZ under controlled conditions. The kinetics, products, and reactivity of CBZ/free chlorine reactions were investigated over the pH range of 5.5-10. Results show that free chlorine reacts with CBZ and the reactivity is pH dependent. Furthermore, the results indicate that temperature affects the reactivity of CBZ with free chlorine. The temperature experiment results were fitted with the Arrhenius equation. The calculated Ea and A values are 48.8 kJ/mol and 1.41x104 s-1, respectively. Four common intermediates were detected based on both UV and mass spectral analysis proposed structures were developed based on m/z from mass spectra. / Master of Science

Very few sewage and industrial waste treatment effluents are free from microorganisms and proteins. Such discharges require further treatment by the receiving stream and consequently lower stream quality. The object of this investigation was to evaluate chlorinated solvent processes for the removal of microorganisms, proteins, and other substances from sewage and other wastes. Six different chlorinated solvents were added to different waste samples in the ratio (by volume) of five percent solvent and 95 percent waste, mixed and allowed to settle for a specified period of time. The efficiency of the solvent extraction process was evaluated in terms of reduction of suspended solids, biochemical oxygen demand, and by increased weight of residue separable by sedimentation. The results showed that the process produced the following effects on settled sewage. Suspended solids were reduced by 85 percent, the weight of residue separable by sedimentation was increased 33 percent, and the biochemical oxygen demand was reduced 49 percent. The process was less effective for the treatment of raw sewage, trickling filter effluent, sewage lagoon effluent, or for separation of activated sludge. The variables investigated were temperature, pH and the solvent waste system. Temperature and pH appeared to have negligible effects on the extraction efficiency. The solvents employed were; chloroform, ethylene dichloride, chlorobenzene, carbon tetrachloride, trichloroethane, and dichloroisopropyl ether. Solvents with low vapor pressures and wastes with low concentrations of suspended solids appeared to be the most efficient system. The addition of 20 percent of butanol (by weight) to trichloroethane appeared to increase the extraction efficiency of trichloroethane. Bacterial counts made indicated that the solvent extraction process was affecting better than 90 percent removal of microorganisms from the waste samples. More research will be needed to completely evaluate chlorinated solvent processes for the removal of microorganisms, proteins, and other substances from sewage and other wastes. / Master of Science

Several aesthetic, health, and plumbing quality issues can arise during new construction or renovation of premise plumbing. There has been little research done on many of these concerns and therefore few guidelines or regulations are in place to protect the health of the consumer or the integrity of the plumbing infrastructure. This work examines common construction practices including: 1) effect of residual construction debris, 2) shock chlorination of new plumbing lines, and 3) lead leaching propensity of new brass ball valves. During installation of plumbing systems, residual chemicals and debris including copper brass particles and flux, can be left in plumbing lines following construction and installation. This debris is considered undesirable from health, aesthetic, and corrosion perspectives. Soldering flux is of particular concern due to its corrosive nature. Experiments were conducted to determine the effects of residual solder flux, PVC glue, and metallic debris and to quantify flushing velocities and durations to effectively remove them from a new plumbing system. A flushing velocity of 3 fps for 30 minutes is needed to remove water soluble flux, while petroleum based flux still persists after extensive flushing at 7 fps. Currently a practice known as shock chlorination, whereby super chlorinated water is used for disinfection, is used in water mains after installation or repair as specified in the ANSI/AWWA C651 Standard. This practice is now starting to be required by some building codes in premise plumbing for new construction. Water mains are typically made of concrete where as premise plumbing using copper or PVC piping. Copper pipe is susceptible to attack by high chlorine, and this reaction will also remove the chlorine residual. There is concern about potential damage to copper from free chlorine and that in some systems targeted residuals of chlorine might not be obtained. Experiments did not detect serious damage to copper pipe, but in some waters it was not possible to meet targeted residual levels of chlorine. The addition of orthophosphate corrosion inhibitor or adjustment of pH can sometimes reduce the chlorine decay rate. Extremely high and persistent lead leaching in a brand new building at the University of North Carolina (UNC) traced to leaded bronze ball valves, prompted an extensive forensic evaluation how existing standards (National Sanitation Foundation Section 8) could allow for installation of products that could create a human health hazard due to high lead. Diffusion of lead from within the device to water in the pipe, high velocity, microbial activity and other factors caused more leaching in practice than would be expected based on NSF testing and normalization factors applied to certify a valve as safe. Moreover, use of flux during soldering of joints, increased lead leaching by orders of magnitude relative to results of NSF testing without flux. / Master of Science

This investigation has led to the following conclusions: 1. Good removals of most bacterial species were observed. 2. Increased length of settling time increased the percent removal of pure cultures. 3. The solvent coagulation process worked best at a pH very near the pH produced by the bacteria during growth. 4. There was no advantage in changing from room temperature. S. proper surface active agents aided in the coagulation of bacteria in the solvent ooagulation process. 6. Almost all of the bacteria in suspension after the coagulation process were not viable. 7. Good removals were observed using the solvent coagulation process on mixed cultures. 8. The chlorinated solvent coagulation process shows promise for commercial operations. / Master of Science

This problem was undertaken to determine the potentialities of chlorine dioxide as an algaecide and as an agent for the removal of tastes and odors from fresh water.

The development of an analytical method for the determination of total organic-bound chlorine (TOCl) produced during the chlorination of municipal wastewater effluents is presented. Sewage effluent from the Denton, Texas municipal treatment plant was chlorinated at high chlorine doses (1000 - 4000 ppm), as well as typical treatment levels. Chlororganics present in the wastewater, before and after chlorination, were concentrated by adsorption on Amberlite XAD-2 macroreticular resin, followed by elution with diethyl ether. After concentration, the extracts were analyzed for TOC1 by microcoulometry. Analysis of wastewater extracts revealed the production of substantial amounts of new chlorinated organics when effluents were treated with chlorine. The method shows good precision and estimated accuracy is favorable.

Thesis (PhD)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: In this study an economical, environmentally friendly, selective and efficient process for the extraction and recovery of [AuCl4]- from aqueous acidic chloride-rich solutions, particularly those aqueous solutions having low concentrations of the precious metal complexes has been investigated. Functionalized poly(styrene-co-maleimide) (PSMI) nanoparticles were synthesized by thermal imidization of the poly(styrene-co-maleic anhydride) (PSMA) copolymer with 3-N,N-dimethylaminopropylamine. Stable water-based dispersions were obtained containing spherical, monodisperse PSMI nanoparticles with a narrow size-distribution and average diameters of 50 ± 5 nm. The specific surface area of the bulk PSMI nanoparticles is 88.1 ± 2.2 m2/g with an average pore diameter of 82.3 Å. 13C NMR, FTIR and elemental analyses confirmed the successful and complete conversion of PSMA into the PSMI derivative. The functionalized PSMI nanoparticles synthesized were investigated as a novel anion-exchange material for the extraction of [AuCl4]- ions from aqueous acidic solutions. Batch sorption studies were carried out as a function of various parameters, such as initial gold concentration, PSMI mass, contact time and agitation rate. The [AuCl4]- extraction occurred with extremely fast sorption kinetics and is dependent on the rate of agitation during the batch sorption process. The functionalized PSMI nanoparticles show a maximum gold loading capacity of 1.76 mmol/g (347.7 mg/g). Langmuir and Freundlich isotherm models were applied to analyze the experimental sorption data. The best model describing the sorption process is given by the Langmuir model. Desorption efficiencies of about 80 % and 93 % were obtained using acidified thiourea (0.25 M thiourea/2 M HCl) and a mixture of 10 M HNO3/0.5 HCl as elutant solutions, respectively. X-ray photoelectron spectroscopy (XPS) analysis unambiguously confirms that the immobilized gold species exists in several oxidation states of 0, +I and +III on the PSMI nanoparticles. This proves that the [AuCl4]- ions initially present in the gold feed solutions unfortunately are subject to a reduction phenomenon on the surface of the functionalized PSMI nanoparticles. The existence of the various gold species contributed significantly to poor desorption efficiencies. In addition to PSMI nanoparticles, micro- to millimeter size PSMI resin beads was prepared by an electrospray methodology. This allows for a wide range of PSMI spherical and quasi-spherical bead diameters of shape to be prepared by manipulation of the experimental conditions employed during the electrospray process, such as the concentration of the PSMI in solution, the capillary tip-to-collector distance, flow rate and the applied voltage. 13C NMR and FTIR spectroscopy analyses show that the electrospray methodology allows PSMI resin beads preparation without any change in chemical composition of the PSMI material. Surface area and porosity analysis shows that 450 μm and 1620 μm PSMI beads selected for use in the gold extraction experiments are microporous and have BET specific surface areas of 2.8 ± 0.4 m2/g and 2.0 ± 0.1 m2/g, respectively. Micro- to millimeter size PSMI resin beads of 450 μm and 1620 μm diameter were tested as potential anion-exchange resins for the extraction of [AuCl4]- from aqueous acidic solutions. The time-dependent studies reveal that the extent of gold uptake increases with an increase in contact time and is dependent on the gold concentration in the [AuCl4]- feed solutions. A maximum loading capacity of 120.7 mg/g and 98.16 mg/g was attained for the 450 μm and 1620 μm resin beads, respectively. The experimental sorption data followed a linear trend consistent with a Freundlich sorption model. This sorption trend for [AuCl4]- suggests that a multi-layer sorption process predominates. Desorption of immobilized gold species from the loaded PSMI resin beads was investigated using various elutants such as HCl, HNO3, thiourea, NaCN and NaOH solutions. The best results were obtained using a mixture of 10 M HNO3/0.5 M HCl as elutant with a desorption efficiency of about 97%. Finally, superparamagnetic magnetite (Fe3O4) nanoparticles with a high degree of crystallinity and phase purity were synthesized by a chemical co-precipitation of Fe2+ and Fe3+ salts. The average diameters of the obtained Fe3O4 nanoparticles were about 7 – 8 nm. The Fe3O4 nanoparticles were coated with oleic acid surfactant molecules and used as seed particles for the preparation of 50 nm diameter magnetic PSMI nanoparticles via an in situ imidization reaction. TEM analysis confirmed that the magnetically responsive PSMI nanoparticles consist of magnetite core-polymer shell structure, although more work is required to perfect such materials. / AFRIKAANSE OPSOMMING: In hierdie studie is ‘n ekonomiese, omgewings vriendelike, seleketiewe en effektiewe proses vir die ekstraksie en herwinning van [AuCl4]- uit suur chloried-ryke oplossings, spesifiek oplossings van lae konsentrasies van edel metal komplekse was bestudeer. Gefunksionaliseerde poli(stireen-ko-maleïmied) (PSMI) nanopartikels was gesintetiseer deur middel van termiese imidisasie van die poli(stireen-ko-maleïk anhidried) kopolimeer met 3-N,N-dimetielaminopropielamien. Stabiele dispersies in water was gevind wat soos sweriese mono-disperse PSMI nanopartikels met ‘n noue partikel-grootte verspreiding met ‘n gemiddelde deursnee van 50 ± 5 nm. Die spesifieke oppervlak area van die massa PSMI nanopartikels is 88.1 ± 2.2 m2/g met ‘n gemiddelde porie-grootte van 82.3 Å. 13C NMR, FTIR en elementêre analiese bevestig die suksesvolle en volledige omskakeling van PSMA na PSMI. Die gefunksionaliseerde PSMI nanopartikels was bestudeer as ‘n nuwe anion-uitruil material vir die ekstraksie van [AuCl4]- ione uit suur oplossings. Stel sorpsie studies was uitgevoer as ‘n funksie van verskeie parameters soos onder andere die goud konentrasie in oplossing, PSMI massa, kontak tyd en ‘n mengings tempo. Die [AuCl4]- ekstraksie gebeur met ‘n geweldige sorpsie kinetika en is afhanklik van die mengings tempo gedurende die stel sorpsie proses. Die gefunksionaliseerde PSMI nanopartikels het ‘n maksimum goud sorpsie kapsiteit van 1.76 mmol/g (347.7 mg/g). Langmuir en Freundlich isoterm modelle was gepas en geanaliseer op die experimentele sorpsie data waarvan die Langmuir isoterm model die data die beste gepas het. De-sorpsie effektiwiteit van ongeveer 80 % en 93% was vekry vir die aangesuurde thiourea (0.25 M thiourea/2 M HCl) en ‘n mengsel van 10 M HNO3/0.5 M HCl as elueer oplossings, onderskeidelik. X-straal foto-elektron spektroskopie (XPS) analiese bevestig ongetwydeld die geimmobileerde goud spesies in oksidasietoestande van 0, +I, en +III op die PSMI nanopartikels. Hierdie is bewyse dat die [AuCl4]- oorspronklik teenwoordig in die goud oplossings is onderhewe auto-reduksie fenomeen op die oppervlak van die gefunksionalieerde PSMI nanopartikels. Die bestaan van verskeie goud spesies dra by tot die power de-sorpsie effektiwiteit van ge-immobiliseerde goud. Bykomend tot die nanopartikels is mikro- tot millimeter grootte PSMI partikels voorberei met ‘n elektro-sproei proses. Hierdie metode stel ons instaat om ‘n wye reeks sferiese en quasi-sferiese PSMI partikel se deersnee voorteberei. Deur die manupulasie van die eksperimentele kondisies gedurende die elektro-sproei proses, soos die konsentrasie van die PSMI in oplossing, die kapilêre punt-tot-ontvanger afstant, vloeispoed en die toegepasde potensiaal. 13C KMR en FTIR spectroskopiese analiese wys dat die elektro-sproei proses die PSMI partikel bereiding toelaat sonder enige veranderinge in die chemiese samestelling van die PSMI materiaal. Oppervlak area en porie-grootte analise wys dat 450lksdfhld en dskl jmm partikels gebruik in die goud ekstraksie eksperimente is mikro-porieës en het spesifieke oppervlak-areas van 2.8 ± 0.4 m2/g en 2.0 ± 0.1 m2/g onderskeidelik. Mikro- tot millimeter grootte poli(stireen-ko-maleimied) (PSMI) partikels van 450 μm en 1620 μm deursnee was getoets as potensieele anion-uitruilings-hars vir die ekstraksie van [AuCl4]- vanuit suur oplossings. Die tyd afhanklike studies gee aanduiding dat die mate van goud opname toeneem met ‘n toename in kontak-tyd en is afhanklik van die goud konsentrasie in die [AuCl4]- oplossings. ‘n Maksimum opname-kapasiteit van 120.7 mg/g en 98.2 mg/g was verkry vir die 450 μm en 1620 μm hars partikels onderskeidelik. Die eksperimentele sorpsie-data volg ‘n lineêre neiging in ooreenstemming met die Freundlich model. Die sorpsie neiging van [AuCl4]- dui aan dat ‘n meervuldige laag sorpsie proses domineer. De-sorpsie van die geimobiliseerde goud spesies vanaf die PSMI hars partikels was bestudeer deur gebruik te maak van verskeie elueermiddels soos HCl, HNO3, thiourea, NaCN en NaOH oplossings. Die beste resultate is verkry deur ‘n mengsel te gebruik van 10M HNO3/0.5M HCl as elueermiddel met n de-sorpsie effektiviteit van ongeveer 97%. Superparamagnetiese magnetiet (Fe3O4) nanopartikels met ‘n hoë graad van kristaliniteit en fase-reinheid was voorberei deur ‘n chemiese ko-neerslagvorming van Fe2+ en Fe3+ soute. Die gemiddelde deursnee van die Fe3O4 nanopartikels was ongeveer 7 – 8 nm. Die Fe3O4 nanopartikels was omhul met oleic suur benatter molekules wat gebruik word as saadjies vir voorbereiding van 50 nm deursnee-magnetiese PSMI nanopartikels deur middel van ‘n imidisasie reaksie. TEM analiese bevestig dat die magnetiese PSMI partikels nanopartikels bestaan uit ‘n magnetiet-kern polimeer-skil struktuur.

Antibiotic resistance profiles of fecal coliform isolated from unchlorinated and chlorinated secondary effluent were determined. Of 332 fecal coliforms isolated from chlorinated effluent a mean of 48% were multiply antibiotic resistant. In contrast, of 347 fecal coliforms isolated from unchlorinated effluent a mean of 29% were multiply antibiotic resistant. Resistance to ampicillin, cephalothin, and carbenicillin were significantly higher in the former than the latter. Randomly selected isolates survived and/or grew in sterile and unsterile effluent retaining resistance patterns for 40 days. Resistance factors were transferred in laboratory medium at frequencies from 0 to 1.2 x 10⁻² (number of recombinants/number of recipients) and in sterile neutralized tertiary effluent at frequencies from 0 to 1.0 x 10⁻⁴. Resuscitative techniques were necessary for optimal recovery of fecal coliforms from effluent using selective media. Antibiotic resistance patterns of fecal coliforms isolated from unchlorinated and chlorinated effluent was not associated with chlorine or heavy metal resistance. Multiply antibiotic resistant fecal coliforms from chlorinated effluent were significantly less sensitive to lytic phage than multiply antibiotic sensitive fecal coliforms from unchlorinated effluent (p < .05). Using group discriminate analysis of data, phage typing techniques were shown to be a potential tool for tracing fecal contamination of groundwater.