Polychlorinated biphenyls (PCBs) are carcinogenic persistent contaminants. Although their manufacturing in North America ceased in the late 1970s, their high heat resistance made their use widespread over their production lifetime. As a result, PCB contamination has occurred globally and in particular has plague brownfield redevelopment in urban environments. The remediation of PCB contaminated soil or sediments has historically been dealt with through the expensive and unsustainable practice of excavation followed by off-site disposal or incineration. One potential technology that has shown some success with on-site remediation of PCB contamination is solvent extraction. Solvent extraction is technically simple; it involves excavating the contaminated soil, placing it in a vessel and adding solvent. The PCBs are extracted by the solvent and the treated soil is returned for use on site. Although successful at removing a large quantity of PCBs from some soils, this technology can be improved upon by extracting additional PCB mass and making the extraction more efficient and suitable for colder climates. This thesis aimed to identify the factors controlling PCB extraction with solvents in order to optimize PCB extraction as it is applied on different soil types and in various climates. The research investigated the impact of elevated moisture contents (≤ 20% by weight) on solvent extraction efficiency, the effects of low temperatures (<5ºC) on solvent extraction, and developed a kinetic model to represent PCB solvent extraction. As past research has shown, weathered PCB in soil is more difficult to remove. Contaminated field samples from Southern Ontario, Canada were used for this work, rather than synthetically prepared samples. The impact of elevated moisture contents and low temperature on extraction efficiency was determined through a series of screening experiments using polar and non-polar solvents at both 20ºC and 4ºC. It was hypothesized that improved extractions may be possible with combinations of polar and non-polar solvents. Based on the results of these screening experiments, a factorial experiment was designed using solvent combinations to further assess the role of moisture contents and low temperatures. The role of PCB mass distribution among grain sizes was also evaluated to see if optimization based on grain size separation is possible. Finally, experiments were performed to generate data suitable for the development of a kinetic model that incorporates key factors affecting solvent extraction. Four suitable solvents for solvent extraction in Ontario were identified through a literature review and these were used for this work: isopropyl alcohol (polar), ethanol (polar), triethylamine (non-polar) and isooctane (non-polar). Triethylamine outperformed isooctane and performed best on its own rather than in combination with polar solvents. An interaction between soil moisture content and choice of polar solvent (isopropyl alcohol versus ethanol) was established: a given polar solvent achieves optimal PCB extraction at a specific moisture content range. Temperature was also identified as significantly influencing PCB extraction. Although it was determined that PCBs were distributed unevenly amongst grain sizes, a simple relationship between grain size and fractional organic carbon or organic content was not found. A simple two-compartment kinetic model was developed which is suitable for predicting the PCB concentrations extracted up to 24 hours. The model incorporates both temperature and soil to solvent ratio in order to estimate PCB concentration extracted.

Polychlorinated biphenyls (PCBs) are carcinogenic persistent contaminants. Although their manufacturing in North America ceased in the late 1970s, their high heat resistance made their use widespread over their production lifetime. As a result, PCB contamination has occurred globally and in particular has plague brownfield redevelopment in urban environments. The remediation of PCB contaminated soil or sediments has historically been dealt with through the expensive and unsustainable practice of excavation followed by off-site disposal or incineration. One potential technology that has shown some success with on-site remediation of PCB contamination is solvent extraction. Solvent extraction is technically simple; it involves excavating the contaminated soil, placing it in a vessel and adding solvent. The PCBs are extracted by the solvent and the treated soil is returned for use on site. Although successful at removing a large quantity of PCBs from some soils, this technology can be improved upon by extracting additional PCB mass and making the extraction more efficient and suitable for colder climates. This thesis aimed to identify the factors controlling PCB extraction with solvents in order to optimize PCB extraction as it is applied on different soil types and in various climates. The research investigated the impact of elevated moisture contents (≤ 20% by weight) on solvent extraction efficiency, the effects of low temperatures (<5ºC) on solvent extraction, and developed a kinetic model to represent PCB solvent extraction. As past research has shown, weathered PCB in soil is more difficult to remove. Contaminated field samples from Southern Ontario, Canada were used for this work, rather than synthetically prepared samples. The impact of elevated moisture contents and low temperature on extraction efficiency was determined through a series of screening experiments using polar and non-polar solvents at both 20ºC and 4ºC. It was hypothesized that improved extractions may be possible with combinations of polar and non-polar solvents. Based on the results of these screening experiments, a factorial experiment was designed using solvent combinations to further assess the role of moisture contents and low temperatures. The role of PCB mass distribution among grain sizes was also evaluated to see if optimization based on grain size separation is possible. Finally, experiments were performed to generate data suitable for the development of a kinetic model that incorporates key factors affecting solvent extraction. Four suitable solvents for solvent extraction in Ontario were identified through a literature review and these were used for this work: isopropyl alcohol (polar), ethanol (polar), triethylamine (non-polar) and isooctane (non-polar). Triethylamine outperformed isooctane and performed best on its own rather than in combination with polar solvents. An interaction between soil moisture content and choice of polar solvent (isopropyl alcohol versus ethanol) was established: a given polar solvent achieves optimal PCB extraction at a specific moisture content range. Temperature was also identified as significantly influencing PCB extraction. Although it was determined that PCBs were distributed unevenly amongst grain sizes, a simple relationship between grain size and fractional organic carbon or organic content was not found. A simple two-compartment kinetic model was developed which is suitable for predicting the PCB concentrations extracted up to 24 hours. The model incorporates both temperature and soil to solvent ratio in order to estimate PCB concentration extracted.

Silver concentrations in natural water are very low and generally require preconcentration prior to instrumental analysis. Solvent extraction and anion exchange methods are the most commonly applied techniques for the determination of Ag in water samples. In this study, solvent extraction and anion exchange techniques are combined and modified to an ¡§organic complexation-acid extraction¡¨ method. The procedure developed involves four steps: (1) a buffer is added and the pH of the solution is adjusted for optimization purpose; (2) APDC and DDDC chelating agents were added and the silver in the solution is organically complexed; (3) the solution was passed through AG-MP1 anion exchange resins and silver complexes and their flocculant were retained and; and (4) acid solutions were used to extract silver from the column for subsequent determination of sliver by a graphite furnace atomic absorption spectrophotometer. After the experiments, the optimal procedures were established as the following: The pH of a 1-L aqueous sample was adjusted to ~4.5 by adding a buffer solution. Aliquots of 2.5-mL solutions containing chelating agents (2% w/v each of APDC and DDDC) were added. After being mixed, the solution was passed through an anion exchange column (AG MP-1) and silver complexes (and their flocculated particles) retained. Two 0.5¡VmL aliquots of 6, 4 and 2 N HNO3 were used to extract Ag from the column, aided by sonication for 3 min during each extraction procedure. The final volume is 3 ml, yielding a concentration factor of ~333. Determination of sliver was done by a graphite furnace atomic absorption spectrophotometer. The detection limit is 1.03 pM. This method was suitable for both freshwater and seawater samples, and was successfully applied for the determination of Ag in coastal and off-shore seawaters collected from coastal region off southwestern Taiwan.

In this study, various techniques of hydrometallurgy and ultrasound-assisted solvent extraction were used to recover the platinum group metals (PGM¡¦s) from a composite sample of honeycomb-type autocatalysts. After they were removed from the converter casings, the autocatalyst substrates were first crushed and then ground by a ball mill. The recovery procedures employed are shown as follows: (1) dissolve PGM¡¦s from ground spent autocatalyst by aqua regia leaching; (2) separate PGM¡¦s from base metals in the aqua regia leachate by metal cementation using zinc powder so that PGM¡¦s can be precipitated out; (3) the PGM¡¦s precipitate was first dissolved by aqua regia, then proceed to remove nitrate and hydrochloride within. The residue was further dissolved in hydrochloride acid as a preparation step for solvent extraction; (4) the PGM¡¦s pregnant solution of hydrochloride acid was treated by solvent extraction and stripping to separate and purify each component of PGM¡¦s. Effects of ultrasound agitation on the efficiency of solvent extraction was also evaluated in this work. Results of aqua regia leaching experiments have shown that the quantity of dissolved PGM¡¦s increased as the solid-to-liquid ratio decreased. The maximum dissolved quantity of PGM¡¦s could be obtained by a 3-hr leaching time. At this stage, the PGM¡¦s recoveries are 80-90% for platinum and rhodium and greater than 99% for palladium. The result of a preliminary test has indicated that acetic acid can not effectively separate the PGM¡¦s and base metals. Thus, the method of cementation by zinc powder was employed to separate PGM¡¦s from base metals. Before cementation, the aqua regia leachate was diluted and pH-adjusted to greater than 2. In so doing, an almost complete cementation (>99%) could be obtained by the least quantity of zinc powder. In addition, the base metals occurred with the PGM¡¦s precipitate have been minimized except lead and zinc. While palladium was extracted by di-n-octyl sulfide (DOS), ultrasound assistance has rendered a complete extraction within a few minutes. At this stage, the extraction efficiency was found to be independent of the HCl concentration. It was found that platinum and rhodium were not extracted by DOS. When platinum was extracted by tri-n-octylamine (TOA) and assisted by ultrasound, rhodium will be extracted at the HCl concentration higher than 4M. Thus, TOA is not an effective chemical for selective extraction of platinum. TOA was then replaced by tributyl phosphate (TBP). Experimental results have indicated that the extraction of platinum using TBP was affected by the HCl concentration. The best result was obtained when the HCl concentration was 5M. Extraction by TBP was found to be fast. It took only 20-30 seconds to reach the equilibrium even with no ultrasound assistance. But multi-stage extractions are generally required to extract platinum completely. Rhodium was found to be not extracted by TBP. After palladium and platinum were extracted, only rhodium was remained in the reffinate. In summary, solvent extraction using DOS and TBP has made it possible to separate palladium, platinum, and rhodium effectively. In the palladium stripping solution almost no base metals was determined. However, zinc and lead were found in the platinum stripping solution and the rhodium-containing raffinate. These base metals should be removed to achieve a better purity for each precious metal. The TCLP (i.e., a leaching test for toxicity) result of the autocatalyst substrate after aqua regia leaching has found to be non-hazardous. However, several streams of wastewater and acid gas generated in the recovery process should be properly managed to avoid the secondary pollution.

The stability of hydrogen peroxide (H2O2) is a critical factor for the brightening of mechanical pulps. Inorganic ions, including Fe, Mn and Cu catalytically decompose H2O2. These troublesome metals promote the rapid transformation of H2O2 to nonselective hydroxyl radicals that degrade the cellulose fibres and decrease yields. / The interaction of aqueous metal•complexes with magnesium metal (Mg°) or bimetallic mixtures of magnesium with either palladium (Pd°/Mg°) or silver (Ag°/Mg°) were optimized to remove metals (Mn, Cu and Fe) from solution with concomitant release of the complexing reagent. The analyte metals were removed by both cementation on the surfaces of the excess Mg° and by precipitation as hydroxides. Overall, the reactions were rapid (3 or 10 min) and very efficient. The accelerators (Ag or Pd) were deposited on the surfaces of the Mg°. In a separate study, the excess of Mg° could be reused to mediate more metals removal without apparent loss of reactivity. Among the other iminodiacetate analogs (CDTA, MEDTA, EGTA, HEDTA, DPTA and MTBE), the EGTA and HEDTA proved to be possible substitutes for both efficient metal removal of Mn, Cu and Fe from solution and efficient release of chelating reagent. The measurement of particle size, performed by laser granulometry, demonstrated that smaller particles of precipitate were generated from metal-EDTA complexes by reaction with NaOH than by reaction with Pd°/Mg° bimetallic mixture. If the suspensions of particles were analyzed in the absence of ultrasound, the particles became aggregated into large flocs (up to 150 mum3 ). The reactivity of the bimetallic mixtures was exploited to remove Cu, Mn, Fe, Zn and Al that had been initially chelated with EDTA or DTPA from a thermomechanical pulp (TMP). After 15 min, the metals had been removed efficiently with the bimetallic mixtures. The EDTA released from the TMP filtrate could be recycled efficiently for a total of three cycles. On the other hand, the DTPA was not released as efficiently. Measurements of turbidity and chemical oxygen demand (COD) indicated no appreciable difference between the pulp samples with either chelating reagent. Residual H2O2 and ISO brightness measurements indicated no apparent differences among pulps that had been treated wi

Chlorinated aromatic compounds are an important group of compounds. Many of them have been produced in large quantities and they are indispensable to technological and societal benefits. But regulatory agencies have tightened regulations on the use and release of chlorinated aromatic compounds because of the scientific understanding of their toxicity, persistence, behavior in the environment and their potential to cause adverse effects on the ecosystem and human health. / Pentachlorophenol (PCP), octachloronaphthalene and decachlorobiphenyl are all highly chlorinated aromatic compounds, of which, PCP has been used mainly as a biocide. Octachloronaphthalene and decachlorobiphenyl don't have practical use, but their congeners have been used widely as chemicals in industry. These compounds are toxic, recalcitrant and bio-accumulated within organisms. As the conventional treatment, incineration of these compounds can cause more serious problems, so that suitable alternatives need to be developed for their detoxification. / When compared with biodegradation or the thermal treatment of these compounds, chemical degradations have several merits. (Abstract shortened by UMI.)

Anatoxin-a (ANTX) is a neurotoxin produced by several freshwater cyanobacteria and has been implicated in the death of livestock and domestic animals from consumption of tainted surface waters. ANTX is unstable under normal conditions and is somewhat problematic to extract and study. Accelerated solvent extraction (ASE) combined with liquid chromatography-mass spectrometry (LC/MS) was used to develop an efficient extraction and analytical method for both ANTX and the more commonly encountered hepatotoxic microcystins produced by cyanobacteria. The effects of nitrogen supply on the cellular production and release of ANTX was investigated in Aphanizomenon issatschenkoi (Ussaczew) Proschkina-Lavrenko (Nostocales). In contrast to the predictions of the carbonnutrient balance hypothesis, the maximum production was observed under moderate N stress. In addition, steady state fugacity-based models were employed to investigate ANTX’s distribution and fate in freshwater ecosytems. ANTX was not found to be very persistent in aquatic ecosystems and did not appear to bioaccumulate in fish, at least not from the dissolved phase.

Pea seeds were tempered at moisture contents of 12.0&amp / #61617 / 0.1, 13.0&amp / #61617 / 0.1, 14.0&amp / #61617 / 0.1 and 15.0&amp / #61617 / 0.3%. The seeds with different moisture contents were then milled and fractioned according to the particle size of 53, 106, 212, 425 and 850 &amp / #956 / m. Tempering the pea seeds (12.0&amp / #61617 / 0.1, 13.0&amp / #61617 / 0.1, 14.0&amp / #61617 / 0.1 and 15.0&amp / #61617 / 0.3%) did not significantly affect the mass and protein fraction in comparison with the pea seeds that are not tempered (11.45&amp / #61617 / 0.05%). For the production of pea protein isolate, aqueous-solvent extraction method was used. The protein was extracted with an alkali solution from the ground pea-seeds and precipitated from the extract by bringing the pH down to isoelectric point (pH=4.5). The precipitated protein was separated from the supernatant by centrifugation. The effects of extraction parameters on the yield of extraction such as pH, particle size, temperature, solvent to solid ratio, and salt were studied. The maximum yields were obtained at these conditions / pH: 12.0 for the alkalinity of the extraction medium, 53 &amp / #956 / m for the particle size, 40&amp / #61616 / C for the extraction temperature, 5.0 for the solvent to solid ratio and 0.0 M for the saline concentration. At these extraction conditions, the maximum protein recovery was 72.75% resulting in a product containing 93.29% protein on a dry basis.

Dissertation (Ph.D.)--Auburn University, 2007. / Abstract. Vita. Includes bibliographic references (p.238-254).

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