Biocides are widely used as a preservative or as an antiseptic agent in consumer care products such as toothpaste, mouthwash, and soaps, as well as in household cleaners and even in textiles due to their high antimicrobial effectiveness. The usage of this compounds results in discharge to wastewater treatment plants and so into surface waters. Their existence in the environment is of importance due to their negative effects on aquatic environment microorganisms and human health in terms of occurrence in surface waters and their fate in wastewater treatment plants. In this scope, this study focuses on occurrence and fate of selected biocides, namely triclosan (TCS) and chlorhexidine (CHD), in wastewater treatment plants and in surface waters. It was aimed to determine the biocides levels in surface water and wastewater in Turkey. For the wastewater treatment plant (WWTP) studies, several WWTPs with different process configurations, namely, Tatlar WWTP, METU WWTP, Kayseri WWTP and Antalya WWTPs were selected. Composite wastewater samples were taken from various points along the WWTPs on a seasonally basis for one year period. For the surface water part, samples were taken monthly from three different sources with different pollution levels, namely, Kesikk&ouml / pr&uuml / Reservoir, &Ccedil / amlidere Reservoir and Eymir Lake for one year period. All water samples were analyzed for their biocide level using liquid chromatography, following solid phase cartridge extraction. As a result of analyses, TCS concentration in surface water samples was detected as in the range of 0.65-11.15 ng/L, 0.86-48.96 ng/L and 0.86-757.7 ng/L for clean, moderately polluted and polluted water sources respectively. The recovery of solid phase extraction analyses for TCS was achieved as %92. CHD concentration was determined as in the range of &lt / 1.33-5.31 ng/L for surface water samples and the recovery of extraction were calculated as %96 for CHD. The concentration of TCS in wastewater samples was measured as in the range of 1.77-94.47 ng/L and 1.40-15.09 ng/L for influent and effluent samples respectively. These ranges became 1.39-10.45 ng/L and &lt / 1.32-2.44 ng/L for CHD. The highest concentrations of biocides were observed in sludge samples with concentrations of 1117-3687 &mu / g/kg and 510-2742 &mu / g/kg for TCS and CHD. Biocide removal efficiency of primary and biological treatment together was reported as % 67.5&plusmn / 8.2 in January 2012 Tatlar WWTP analyses.

The aim of this study was to develop methods for sample preparation for 8-OHdG in blood plasma samples with different solid phase extraction techniques using HPLC with an elec- trochemical detector. The solid phase extraction cartridges used were Chromabond® C18, Oasis® MAX, and three types of SupelMIPTM cartridges for chloramphenicol, riboflavin, and nitroimidazoles. The SupelMIPTM cartridges are based on molecularly imprinted polymers- technique. The separation of 8-OHdG in samples extracted from blood plasma was carried out with a Thermo Quest Hypersil Division ODS column (250 mm × 4 mm, 3μm I.D.) and methanol:buffer (10:90, v/v) as mobile phase. Recovery and selectivity was studied for the different solid phase extraction methods. The highest recovery was obtained using the Chromabond C18 cartridge with a recovery of 92%, and CV coefficient 9.5% (n = 4). 8-OHdG could not be extracted on MIP-cartridges for chloramphenicol or riboflavin, but was retained on MIP columns for nitroimidazoles, and the highest recovery was 49%.

This research investigate the matrix effect, operation time, cost and solvent comsumption for triarylmethanes and corresponding metabolites in different aquaculture products by different extraction methods. Triarylmethane was determined by LC-ESI-MS/MS in positive mode. The analytical method validation were followed the regulation of 2002/657/EC. HPLC separation was conducted with the RP-18 column. The mobile phases consisted of 0.5 mM ammonium acetate buffer (pH 3.8, adjusted with acetic acid) ¡V acetonitrile (contained 0.1% formic acid) solution. The ratios of standard deviation to average residual time for all compounds are less than 0.05. The ion ratio is stable and allowed by the regulation of 2002/657/EC. The regression constant of calibration curve is in the range from 0.998 to 0.999. The CC£\ for MG, LMG, CV, LCV are 0.09 ¡Ó 0.05, 0.19 ¡Ó 0.14, 0.15 ¡Ó 0.13, 0.15 ¡Ó 0.10 £ggkg-1, respectively. The CC£] for MG, LMG, CV, LCV are 0.09 ¡Ó 0.05, 0.19 ¡Ó 0.14, 0.15 ¡Ó 0.13, 0.15 ¡Ó0.10 £ggkg-1, respectively. The results for SPE and liquid-liquid extraction are not significantly different; the liquid-liquid extraction have shorter operation time, cheaper cost and less solvent consumption in comparison with SPE.

A LC-MS/MS method for the analysis of alkylphenol polyethoxylates in environmental waters was developed in this study. Preatment procedures including liquid-liquid extraction and solid phase extraction were compared, it¡¦s concluded that solid phase extraction is the more suitable way due to higher recovery and better stability for the analytical results. The recovery of nonylphenol polyethoxylate and octylphenol polyethoxylate were 62.3-110.7 % and 64.9-112.0 %, limit of detection were 17.60-174.9 ng/L and 7.40-53.56 ng/L. Enviromental water samples were collected from eight sampling sites along Love River in Kaohsiung City to investigate the contents of alkylphenol polyethoxylates. The highest concentration of total alkylphenol polyethoxylates was observed at Ming-Cheng Bridge which located at the upstream of Love River. For all of the analyzed compounds, the concentration of octylphenol tetraethoxylate (40.46 £gg/L) was the highest in all of the sampling sites. It¡¦s also noticed the concentration of octylphenol polyethoxylate (20.11 £gg/L) was higher than that of nonylphenol polyehtoxylate (128.04 £gg/L).

In April and June 2012, environmental water samples were collected from fourteen sampling sites in Hengchun peninsula to investigate the contents of alkylphenol polyethoxylates. A solid phase extraction combined with LC-MS/MS method for the analysis of alkylphenol polyethoxylates in environmental waters was developed in this study. The mobile phase used methanol gradient elution with deionized water. The recovery of nonylphenol polyethoxylate and octylphenol polyethoxylate were 68~94 % and 65~93 %, limit of detection were 1.89~54.20 ng/L and 0.44~39.31 ng/L, limit of quantitative were 6.29~181 ng/L and 1.48~131 ng/L. The SsuChung river contents of NPEO and OPEO were 15.64~36.29 £gg/L and 3.14~7.37 £gg/L. The Paoli river contents of NPEO and OPEO were 16.65~76.41 £gg/L and 5.66~18.80 £gg/L. The Hou Bay contents of NPEO and OPEO were 34.79~66.72 £gg/L and 7.77~19.03 £gg/L. The Shihniou river contents of NPEO and OPEO were 26.67 £gg/L and 6.68 £gg/L. The Wanli Tong, Baisha, Houbi Lake, South Bay, Caesar and Siangjiao Bay contents of NPEO and OPEO were 14.17~48.82 £gg/L and 3.88~14.79 £gg/L. The dry season concentration contents of alkylphenol polyethoxylates were high than the wet season. The concentration of nonylphenol polyethoxylate was higher than that of octylphenol polyehtoxylate.

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Concentrations of 17 organochlorine and 14 organophosphorus pesticides were measured in 27 ground and 11 surface water samples collected from a heavily agricultural area, Kumluca, in spring and fall seasons of 2005. The samples were preconcentrated by Solid Phase Extraction. GC-ECD and GC-NPD systems were used for quantitative determination of organochlorine and organophosphorus pesticides respectively. The quality check/quality assurance tests were performed by the analysis of field and laboratory blanks, standard reference materials, spiked control and sample matrices, surrogate standards, sampling and analysis replicates. It is observed that, sample matrix lowers average percent recoveries from 89% to 76%. The uncertainties of measurements were calculated to determine major factors affecting the analysis results. It was observed that uncertainty arising from extraction procedure was generally the highest. The most commonly observed pesticide was endosulfan (70%) and chlorpyriphos (53%) for organophosphorus and organochlorine pesticides. The highest average concentration was observed for heptachlor (26 ng/L) and fenamiphos (184 ng/L). Generally pesticides were detected more often in surface waters, where the concentrations were also higher. The concentrations of organophosphorus pesticides in spring, and organochlorine pesticides in fall season were higher. The high occurrences and detection of degradation products of chlorinated pesticides clearly indicate their intense use before 1980s. It is shown that, in Kumluca environment, degradation of these pesticides mostly occurs in surface waters. It is observed that agricultural activities affect water quality in the region. The total concentration limit (500ng/L) was exceeded for 27% of surface and 14% of ground water samples, at least once in both seasons. The legal limit for a single pesticide (100ng/L) was exceeded by 32 % of surface, 24 % of ground water samples.

The origin of fluorous interaction was explored and experimentally examined based on both HPLC and CEC data in this project. It was found that the selective fluorous interaction is a kind of reduced instantaneous or induced dipole interaction compared to the hydrophobic interaction. A series of FPPM preparation parameters were optimized. The optimized FPPM column can resolve the components in a manner that was otherwise not possible with its non-fluorous (hydrocarbon) counterpart. Following, the CEC separation of fluorous analytes on FPPM stationary phase based upon fluorous-fluorous interaction was realized for the first time. It was also found that, quantitatively, hydrophobic stationary phases have better methylene selectivity (〖 α〗_(-CH_2-)), while fluorous stationary phases have better perfluoromethylene selectivity (〖 α〗_(-CF_2-)). Thermodynamically, ∆G_(-CF_2- → -CF_2-)^° : ∆G_(-CH_2- → -CH_2-)^° (Gibbs free energy change of transferring a –CF2– unit to pure fluorous stationary phase versus Gibbs free energy change of transferring a –CH2– unit to pure hydrophobic stationary phase) is approximately equal to 8:1. A new concept, hypothetical water percentage (HWP) based on the comparison of 〖 α〗_(-CH_2-) and〖 α〗_(-CF_2-) was proposed for the first time to quantitatively evaluate the hydrophobicity/fluorophilicity of a stationary phase. A stationary phase can be classified as fluorous stationary phase when the HWP is less than 0 (more negative indicates more fluorous), or as a hydrophobic stationary phase when the HWP is larger than 100. For the range between 0 and 100, the stationary phase can be treated as either fluorous or hydrophobic due to the similar values of〖 α〗_(-CH_2-) and〖 α〗_(-CF_2-). Fluorous tagged peptides and proteins (up to 5800 Da) were effectively separated from their non-fluorous counterparts on the FPPM stationary phase in capillary-based columns and detected both on-line with ESI-MS and off-line with MALDI-MS. Finally, the FPPM solid-phase extraction (SPE) stationary phase was transplanted from the capillary to a microchip format. This microchip exhibits the merits of both selective fluorous interaction and micro total analysis system (µTAS). / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-11-19 23:11:16.636

Sample preparation has a critical role as a first step in analytical processes, especially in bioanalysis and environmental analysis. A good sample preparation technique should be robust and stable, regardless of the sample matrix. The aim of this thesis is to design and synthesize molecularly imprinted polymers that can be used in various sample preparation techniques, such as on-line MEPS, on-line SPE and on-line monolithic pre-columns used for the extraction of drugs, hormones, and cancer biomarkers from human plasma and urine samples. Additional aim was to provide full automation, on-line coupling, short sample preparation time and high-throughput. In this thesis MIP in MEPS was used on-line with liquid chromatography-tandem mass spectrometry (LC/MS/MS) for the determination of sarcosine in human urine and plasma samples. The method was fully automated and the packed sorbent could be used for about hundred extractions. In additional work a coated needle with MIP-Sol-Gel as thin layer was prepared and used for the microextraction of bilirubin from human plasma and urine. Small sample volumes could be handled and the validation of the method showed that the method was robust and selective. In a further work MIP-SPE on-line with HPLC was used for the extraction and determination of dextromethorphan in human plasma samples. MIP-SPE showed a good selectivity and high recovery (87% - 92%). On-line MIP monolithic pre-column was prepared and used in a coupled system for the extraction of tramadol in human plasma and urine samples. The MIP monolithic pre-column showed good selectivity and high extraction recovery was obtained (91-96%). The extraction and analysis of human insulin in plasma and pharmaceutical formulation solutions were carried out using MIP-SPE on-line with HPLC. The validation of the method showed that the method was accurate and robust. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Submitted.</p>

Although the benefits of ICP-MS are well documented, the determination of analytes at low levels in high concentrations of matrix elements has proved difficult. As ICP-MS is a 'flow into' instrument the deposition of salts throughout the system is a common cause of significant loss of signal. The application of desolvation of aluminosilicate samples, to aid in the production of more robust plasma conditions, was investigated to increase the efficiency of the ICP in processing the sample. The performance of the ICP-MS was monitored with different cone arrangements and by running the skimmer cones at elevated temperatures. An alternative to modification of the instrument is to employ chemical modification of the sample and hence the separation of Au and Pt from an aluminosilicate matrix via the use of solid phase extraction (SPE) columns were investigated as a means of dealing with high levels of dissolved solids. OVB based SPE columns were found to give high retentions of Au and Pt when chelated with ammonium pyrrolidinediethylcarbamate (APOC). A second alternative that avoided digestion of the aluminosilicate matrices, was to carry out the analysis using laser ablation (LA). LA-ICP-MS is becoming increasingly used for trace elemental analysis but as yet no universal calibration method is available. The general problems associated with matrix matched standards are inherent as the ablation mechanism and plasma conditions can differ dramatically with very small changes in matrix composition. Hence the addition of chromophores was employed to increase the absorption of the laser energy. The use of vanillic, nicotinic and pyrazinoic acid were used to improve the ablation of pressed powder discs at the laser wavelength of 213 nm. Synthetic aluminosilicate discs and standard additions were both employed for the calibration and determination of Ti.