Two new analytical methodologies were developed for chlorine and bromine stable isotope analyses of inorganic samples by Continuous-Flow Isotope Ratio Mass Spectrometry (CF-IRMS) coupled with gas chromatography (GC). Inorganic chloride and bromide were precipitated as silver halides (AgCl and AgBr) and then converted to methyl halide (CH3Cl and CH3Br) gases and analyzed. These new techniques require small samples sizes (1.4 µmol of Cl- and 1 µmol of Br-). The internal precision using pure CH3Cl gas is better than ∓0.04 ‰ (∓STDV) while the external precision using seawater standard is better than ∓0.07 ‰ (∓STDV). The internal precision using pure CH3Br gas is better than ∓0.03 ‰ (∓STDV) and the external precision using seawater standard is better than ∓0.06 ‰ (∓STDV). Moreover, the sample analysis time is much shorter than previous techniques. The analyses times for chlorine and bromine stable isotopes are 16 minutes which are 3-5 times shorter than all previous techniques. Formation waters from three sedimentary settings (the Paleozoic sequences in southern Ontario and Michigan, the Williston Basin and the Siberian Platform) were analyzed for 37Cl and 81Br isotopes. The δ37Cl and δ81Br values of the formation waters from these basins are characterized by large variations (between -1.31 ‰ and +1.82 ‰ relative to SMOC and between -1.50 ‰ and +3.35 ‰ relative to SMOB, respectively). A positive trend between δ81Br and δ37Cl values was found in all basins, where an enrichment of δ81Br is coupled by an enrichment of δ37Cl. In the Paleozoic sequences in southern Ontario and Michigan, the δ37Cl and δ81Br signatures of formation water collected from northwest of the Algonquin Arch are distinct from those collected from southeast of the Arch. All of the brines from the northwest of the Algonquin Arch are characterized by depleted isotopic values in comparison with the isotopic values from the brines from southeast of the Arch. The δ81Br signatures of the two brines show total separation with no overlaps. The δ37Cl values show some overlap between the two groups. One of the scenarios that can be put forward is that the Arch forms a water divide, where sediments southeast of the Arch are dominated by Appalachian Basin formation waters, and the sediments located northwest of the Arch are dominated by the Michigan Basin formation waters. The δ81Br and δ37Cl signatures of the Williston Basin brines suggest the existence of several different brines that are isotopically distinct and located in different stratigraphic units, even though they are chemically similar. The relatively wide range of δ37Cl and δ81Br of the formation waters suggests that the ocean isotopic signatures were variable over geologic time. A seawater temporal curve for δ81Br and δ37Cl was proposed with a larger variation of δ81Br in comparison with δ37Cl. The isotopic variations of these two elements agree very well with 87Sr/86Sr seawater variation during the same period. In general, the use of chlorine and bromine stable isotopes can be very useful in assessing the origin and the evolutionary processes involved in evolving formation waters and also in distinguishing different brines (end members). Furthermore, they can be employed to investigate the hydrogeological dynamics of sedimentary basins.

Isotopic methods have been developed over the last 10 years as a method for determining chemical interactions of chlorinated solvents. These methods are especially promising for. This study attempts to employ and develop compound specific isotopic analyses of TCE and cDCE, along with chemical data, to characterize the degradation of TCE in a fractured bedrock aquifers. The Smithville site is a contaminated field site with extremely high levels of TCE contamination that is currently undergoing monitored remediation. From December 2008 until April 2010 extended samples were collected from the site to provide additional data analyses including isotopic data. The redox conditions at the site are anoxic to reducing, with sulfate reduction and methanogenesis as dominant terminal electron accepting processes. Redox data indicates that well electrochemical conditions are highly variable within the site, including areas near the source zone that not very reducing. Documented changes in groundwater conditions to much more reducing environments indicate that oxidation of organic matter is occurring at the Smithville site in select wells. Chemical analyses of TCE, DCE, VC, ethene and ethane are employed determine whether reductive dechlorination was occurring at the site. Results of field testing indicate that many wells on site, especially in the proximity of the source zone, dechlorination products were found. The isotopic data had a high range in both carbon and chlorine isotopes. Chlorine isotopic data ranges from a δ37Cl(TCE) of 1.39 to 4.69, a δ37Cl(cDCE) of 3.57 to 13.86, a δ13C(TCE) of -28.9 to -20.7, and a δ13C(cDCE) of -26.5 to -11.82. The range in values indicate varying degrees of degradation throughout the site, with the same wells grouping together. Combined chemical, redox and isotopic data shows that degradation seems to be a removal process for TCE at the Smithville site. Concentrations of chemicals created as a result of TCE degradation verify degradation, especially in wells 15S9, R7 and 17S9. Historically production of DCE in significant amounts, above 1.0 ppb, was observed to only occur after 2003. In addition to this, DCE data shows that the percentage of DCE made up of cDCE is above 96%. This indicates that microbes most likely mediate the processes that formed DCE from TCE. The linear regression of the delta-delta plot for isotopic TCE data shows line that is likely a direct function of the carbon and chlorine isotopic fractionation imparted upon the original TCE released. The slope found is consistent with data collected from other studies though cannot be applied to determining the process directly given the range of variability in isotopic field data.

This thesis presents the potential of integrating chemical and biological treatment technologies for the removal of high concentrations of phenol in a bioremediation medium. High concentrations of phenol in wastewater are difficult to remove by purely biological methods. Chemical oxidation is one way to treat high concentrations of phenol but complete oxidation is not always possible or will make the treatment process uneconomical. An experimental design approach, based on central composite rotatable design (CCRD) was used to evaluate the effects of process parameters on phenol oxidation by Fentons reagent and chlorine dioxide. Performance of the chemical oxidation was evaluated by determining the percentage of phenol oxidized at equilibrium. The reaction mechanism for the oxidation of phenol by Fentons reagent was proposed based on identification of the intermediate compounds.<p> The effects of H₂O₂ concentration (2000 to 5000 mg L^-1) and FeSO₄.7H₂O concentration (500 to 2000 mg L^-1) were investigated on phenol oxidation and optimal concentrations of H₂O₂ and FeSO₄.7H₂O for complete oxidation of 2000 mg L^-1 phenol in medium were found to be 4340 mg L^-1 and 1616 mg L^-1, respectively, at 25°C and pH 3. The main oxidation products were identified as catechol, hydroquinone and maleic acid.<p> In the case of phenol oxidation by chlorine dioxide, the effects of chlorine dioxide concentration (500 to 2000 mg L^-1), temperature (10 to 40°C) and pH (3 to 7) on the oxidation of 2000 mg L^-1 of phenol were determined. The optimal concentration of chlorine dioxide to completely oxidize 2000 mg L^-1 of phenol was 2000 mg L^-1. The other parameters did not significantly affect the oxidation over the ranges studied. The main oxidation products were identified as 1,4-benzoquinone and 2-chloro-1,4-benzoquinone.<p> Finally, the biodegradation of 1,4-benzoquinone, the main oxidation product of phenol oxidation by chlorine dioxide, was studied in batch and continuous systems using Pseudomonas putida 17484 in two dose McKinneys medium. The effects of 1,4-benzoquinone concentration and temperature were studied on biodegradation of 1,4-benzoquinone in batch reactors. Under optimal conditions, it was found that 150 mg L^-1 1,4-benzoquinone could be successfully biodegraded at 15°C. In a continuous reactor operating at 15°C the highest removal rate with 500 mg L^-1 of 1,4-benzoquinone was found to be 246 mg L^-1 h^-1. The values of µmax, Ks and yield were also determined as 0.74±0.03 h^-1 and 14.17±3.21 mg L^-1 and 2x10¹³ cell mg^-1, respectively.

Research has shown that formation of chlorinated organic matter occurs naturally and that organic chlorine is as abundant as the chloride ion in organic soils. A large number of organisms are known to convert inorganic chloride (Clin) to organic chlorine (Clorg) (e.g. bacteria, lichen, fungi and algae) and some enzymes associated to these organisms are capable of chlorinating soil organic matter. The aim with the study was to compare organic matter chlorination rates in soils from several different locations dominated by either coniferous forest or pasture. Soil from eight samples sites in the southern of Sweden were incubated at 20°C with addition of 36Clin in a 138 days long radiotracer experiment. The results show that transformation of 36Clin to 36Clorg occurred and that the amounts of 36Clorg increased over time. The chlorination rate was higher in the samples from coniferous forest than in samples containing pasture soil, where the specific chlorination rate was 3-4 times smaller. This study contributes new information about chlorination in various soil types and soil from different locations in southern central Sweden. The similarity between the chlorination rates measured in coniferous forest soils so far indicate that up scaling to regional estimates may be less problematic than expected.

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The pollution of soil and groundwater have increased due to the leakage of ptrolium products and organic chemicals in the country recently,and Taiwan face with small region and dense population,so the pollution maybe exposed through relevant way such as quality of water,soil,air,crop and fish and so on to affect human health and cause risk of jeopardise directly or indiretly. The study is to aimed at chlorinated compounds for domestic,and use methods of risk assessment to analyze necessity and urgency of renovation for be contaiminted compound and downstream influence.And then according to result to make relevant management strategies and projets to control risk level and influence for contaiminated compound. In this study,we collect information relate to case,in accordence to health and risk assessment methods for soil and groundwater contaminated sites and some softwares of CRYSTAL BALL and BIOCHLO by Environmental Protection Bureau to estimate the site which was evaluated chlorinated compound (trichloroethylene,TCE),and considerate whether they affect residents healy nearby,use some hydrogeological survey of sites to process second-level health risk assessments. First,use commercial software of CRYSTAL BALL execute uncertainty and sensitivity analysis. Not only does the analysis probe into overall parameters variaty how to affect risk value but also they process analysis and results by different combinations of paremeter.From this result, we can confirm that the large parameter values for affecting risk is transmission of pollutants and is similar to previous studies assessment and analysis.Other parameter cause less influence for risk variaty such as age level of receptor,group,the way of contact,time and water quntity.The study discovers TCE pollutants concentration will make change of risk value by accompany with groundwater move to downstream distance. That means receptor of distance of contamination resource cause large influence. The far distance represents can product the larger function for TCE pollutant, and causes less cancer risk for receptor, conversely, it causes higher cancer risk. Subsequently, we also use BIOCHLOR assessment software by U.S.A Enviromental Protection Bureau. from the result to determine whether the site have potential of anaerrobic reductive dechlorination or not and estimate natural attenuation possibility.The actual situation of the site gets the three score in the weight total.This display do not prove that chlorinated compounds can procedd biogical decomposition in the anaerobic invironment without more correct value in the stage.We recommend looking for another renovations. The study selects more important sensitive parameters through risk assessment result for the site and work out the way of renovations which is suitable for this case by schedule of object. The investigation has found that residents indeed extracted groundwater for agriculture irrigation, but not drank water directly. In order to avoid the worst situation happens from the view of risk, we will consider two aspects of regulation and technology for plan. First, in order to administration control for the aspect of regulation we will consider how to prohibit residents to extract groundwater effectively. For instance, prohibit or limit to set up underground well, provide substitute drink water, set up notice sign and underground water quality monitor measure regularity. Second, for the sake of preventing pollutant group spread and adopt measure for the aspect of technology, for example pollution remediation technology (include soil gas extraction, air injection method at present) and containment control technology (include hydraulic containment, permeability reactive barrier, natural biological remediation, etc) to manage effectively possible events in the site and prepare well prevention in advance. We also adopt good communication with local residents to let residents understand executive content for renovation and reduce their resistance in favor of making progress for renovation and achieve risk management objective.

The purposes of this study include: (1) investigating the reasons why drinking water quality degrades during transportation in the distribution system and developing an easy and effective tool to evaluate the status of distribution system; (2) investigating residents¡¦ satisfaction with advanced treated drinking water. It is found that the main reason of drinking water degradation is that most people don¡¦t flush the drinking water storage facilities routinely. It is also found that although most respondents are satisfied with advanced treated drinking water, nearly 40% of local residents still buy bottle water instead of drinking tap water. Therefore, Taiwan Water Supply Corp. (TWSC) should let people know the importance of flushing water storage facilities routinely and what TWSC has done to improve drinking water quality. The LSI (Langelier Saturation Index) of most water samples is negative, which means that the drinking water is corrosive when too much hardness is removed to comply with the regulations. A simple, efficient and cost-effective method is developed to provide TWSC sufficient information to solve the problems regarding water quality degradations in distribution systems. By using contour maps of different water quality parameters, TWSC can easily identifies locations with potential problems and easily assesses the necessity and appropriate locations of building re-chlorination stations, even though the lack of information regarding pipeline material, hydraulic conditions, thickness of biofilm¡Ketc.

Quality of municipal water is sustained by addition of disinfectant, generally chlorine, to the water distribution network. Because of health problems, chlorine concentration in the network is limited between maximum and minimum limits. Cancerogenic disinfectant by-products start to occur at high concentrations so it is desired to have minimum amount of chlorine without violating the limit. In addition to the health issues, minimum injection amount is favorable concerning cost. Hence, an optimization model is necessary which covers all of these considerations. However, there are uncertain factors as chlorine is reactive and decays both over time and space. Thus, probabilistic approach is necessary to obtain reliable and realistic results from the model. In this study, a linear programming model is developed for the chance constrained optimization of the water distribution network. The objective is to obtain minimum amount of injection mass subjected to maintaining more uniformly distributed chlorine concentrations within the limits while considering the randomness of chlorine concentration by probability distributions. Network hydraulics and chlorine concentration computations are done by the network simulation software, EPANET.

Propylene epoxidation reaction was investigated on catalytic surfaces of chlorinated copper(I) oxide and ruthenium(IV) oxide using periodic density functional theory (DFT). Cu2O(001) and (110) surface of RuO2 was selected to generate chlorinated surfaces to be used in the study. Besides epoxidation, other reactions that compete with epoxidation were also studied such as formations of allyl-radical, acrolein, acetone on chlorinated Cu2O(001) and formations of propionaldehyde, allyl-radical and acetone on chlorinated RuO2(110) surface. Path of each reaction was determined by CI-NEB method and transition state analyses. Generally accepted stable surface intermediate mechanism was utilized in reactions to final products. The surface intermediate favorable on the surfaces in this study was determined to be the intermediate that is not preferable on metallic surfaces under low oxygen. On chlorinated Cu2O(001) surface, formation of propylene oxide, acetone and acrolein have higher probability than gas phase allyl-radical since the desorption energy of allyl-radical was calculated to be 70kcal/mol which is a relatively high value. In fact it is desirable since gas phase allyl-radical is known to be the precursor of combustion products. On chlorinated RuO2(110) surface, desorption Propylene epoxidation reaction was investigated on catalytic surfaces of chlorinated copper(I) oxide and ruthenium(IV) oxide using periodic density functional theory (DFT). Cu2O(001) and (110) surface of RuO2 was selected to generate chlorinated surfaces to be used in the study. Besides epoxidation, other reactions that compete with epoxidation were also studied such as formations of allyl-radical, acrolein, acetone on chlorinated Cu2O(001) and formations of propionaldehyde, allyl-radical and acetone on chlorinated RuO2(110) surface. Path of each reaction was determined by CI-NEB method and transition state analyses. Generally accepted stable surface intermediate mechanism was utilized in reactions to final products. The surface intermediate favorable on the surfaces in this study was determined to be the intermediate that is not preferable on metallic surfaces under low oxygen. On chlorinated Cu2O(001) surface, formation of propylene oxide, acetone and acrolein have higher probability than gas phase allyl-radical since the desorption energy of allyl-radical was calculated to be 70kcal/mol which is a relatively high value. In fact it is desirable since gas phase allyl-radical is known to be the precursor of combustion products. On chlorinated RuO2(110) surface, desorption observed to be possible on chlorinated RuO2(110) surface but not possible on chlorinated Cu2O(001). When activation barriers and desorption energies of all possible reactions are compared on chlorinated RuO2(110) surface / gas phase propylene oxide generated directly seems as the preferable product with allylradical although it was computed to have high desorption energy. Comparison of activation barriers obtained in this study on chlorinated Cu2O(001) with the barriers of nonchlorinated surface revealed chlorine slightly increases the activation barrier of unwanted allylic hydrogen stripping and hence slightly decreases the probability of occurance. When chlorine is placed closer to reaction site, activation barrier of allylic hydrogen stripping reaction increases further. The effect of chlorine might be electronic since the charge of oxygen at reaction site slightly becomes less negative when the place of chlorine gets closer to the reaction site on the surface. Similar comparison between chlorinated and nonchlorinated RuO2(110) surfaces revealed that chlorine addition does not improve the surface toward propylene oxide formation, rather it is detrimental as chlorine addition caused a decrease in unwanted allylic hydrogen stripping reaction.