Synthetic musk compounds are artificial organic compounds with a smell similar to the odor of a natural musk. The most recently discovered and also the least known group of artificial musks is linear musk compounds. These substances are now often used in cosmetics, personal care products, detergents and various cleaning products. They have leaked into all the major environment components, especially into the hydrosphere. There has been great attention drawn to synthetic musk compounds in the last few years because of their environmental impact. The aim of this thesis is to identify twelve linear musk compounds (linalool, 2-cyclohexylethanol, fresco menthe, citronellol, HSA, isobornyl acetate, arocet, aroflorone, allyl cyclohexyl propionate, lilial, isoamyl salicylate and hexylcinnamic aldehyde) in waste water samples. The samples were taken at three different waste water treatment plants (WWTP) in South Moravian region (WWTP Brno-Modřice, WWTP Luhačovice and WWTP Hodonín). Each of these treatment plants has a different equivalent number of inhabitants. At first, a working method was optimized, then applied on real waste water samples. Solid-phase microextraction (SPME) technique was used for the extraction of analytes. Gas chromatography–mass spectrometry (GC/MS) was then used for identification and quantificaton of the studied compounds.

Polychlorinated biphenyls (PCB) represent relevant persistent organopollutants of the environment and the estimated amount of PCB released into the environment is 750000 metric tons. White-rot fungi have been studied for long time due to their degradative potential toward various aromatic pollutants and it is known that these fungi are able to decompose PCB in vivo. Biodegradation of PCB by the fungus Pleurotus ostreatus was studied in the frame of this work. A high degradative efficiency of P. ostreatus was observed in the first set of experiments, even in the presence of relative high amount of added PCB. Fungus was able to transform 780±50 µg out of the intial amount 1000 µg in 20 ml of a cultivation media within 42 days. A decrease in toxicity was recorded during the degradation that suggests the suitability of this organism for a practical use in decontamination. In vitro experiments with purified laccase induced with Cu2+ from this fungus did not prove any participation of the enzyme in the first step of PCB transformation. The enzyme did not show an ability to degrade PCB even after purification from cultivation media containing PCB. It was found that the first step of PCB transformation can be performed by an intracellular process with microsomal fraction. A degradation of 44-67% was observed for...

Master’s thesis deals with a determination problem of ignitable liquids from fire debris. The aim of this work is to introduce the properties of used fire accelerants and to give an overview and evaluation of the various techniques which can be conducive to the fire investigator. Determination of fire accelerants from fire debris was made by the technique of solid phase microextraction (SPME) with subsequent chemical analysis by GC/MS. Based on the chromatographic results were established the target compounds and reconstructed ion chromatograms which are typical for some kinds of flammable liquids. There were used gasoline, diesel, kerosene and technical gasoline (white spirit) as the fire accelerants. This work also deals with the influence of interfering products in fire debris analysis, including their identification and characterization. Different kinds of substrates were burned, extracted and analyzed in order to identify all the interfering products that they may release.

Acute indoor concentrations of benzene and ethanol were evaluated in the California Polytechnic State University San Luis Obispo’s pilot winery workroom. Air samples were collected during four different wine-making activities: fermentation, fermentation with Brix content testing, post-alcoholic fermentation pressing, and storage/finishing. Average workroom benzene concentrations ranged from 0.05 to 0.12 mg/m3. Ethanol concentrations in the winery workroom varied with the activity, ranging from 0.9 to 12 mg/m3. Pressing and fermentation with Brix content testing both led to higher indoor ethanol concentrations than fermentation without Brix content testing and storage/finishing. Tracer gas decay air exchange tests were conducted to determine the air exchange rate of the winery workroom. A single-space mass-balance model was used to estimate the air exchange rate for the entire workroom. The calculated air exchange rates were correlated with wind speeds and wind direction to create a linear model estimating air exchange rates based on wind speed. These air exchange rates and the indoor concentrations of ethanol were used with the single-space mass-balance model to calculate an ethanol emission rate for each activity. Total estimated ethanol emissions for the four activities were 3.1 lbs. ethanol per 1000 gallons of wine produced.

One of the main problems encountered in chemical analysis operations in the field is collecting sufficient sample from the source and transferring that sample to the measurement instrument for fast separation and identification. I have been involved in developing a field-portable gas chromatography-mass spectrometry (GC-MS) system with solid phase microextraction (SPME) sampling for point detection of chemical agents. The objective is to minimize the analysis time between sampling and detection of a potential chemical threat. SPME offers a convenient means for sampling gaseous and liquid samples, concentrating the analytes, and transferring the analytes to the injection port of a GC system for separation and identification. GC-MS has advantages of high efficiency, speed, and applicability for field analysis. Work was done to optimize the SPME fiber coating, capillary column dimensions, and GC operating conditions to provide complete analysis within 3 minutes. Since isothermal operation of the GC was a prior requirement, many components in the chromatograms were unresolved. Therefore, a peak de-convolution algorithm was applied to allow for identification and quantitation of poorly resolved and often completely obscured trace components. Details of the instrumentation and optimization of operating conditions are described in this thesis.

The ability to rapidly detect and identify hazardous analytes in the field has become increasingly important. One of the most important analytical detection methods in the field is gas chromatography-mass spectrometry (GC-MS). In this work, a hand-portable GC-MS system is described that contains a miniature toroidal ion trap mass analyzer and a low thermal mass GC. The system is self-contained within the dimensions of 47 x 36 x 18 cm and weighs less than 13 kg. Because the instrument has a small footprint, it was used as the detector for an automated near-real-time permeation testing system. In permeation testing, materials that are used to make individual protective equipment such as gloves, masks, boots, and suits are exposed to hazardous analytes to determine how long the equipment can be worn safely. The system described herein could test five samples simultaneously. A multi-position valve rotated among the various sample streams and delivered time aliquots into the MS for quantitation. Current field air sampling techniques suffer from long desorption times, high pressure drops, artifact formation and water retention. These disadvantages can be avoided by concentrating the analytes in short open tubular traps containing thick films. There are several advantages to using polymer coated capillaries as traps, including fast desorption, inertness and low flow restriction. An air sampling trap was constructed utilizing open tubular traps for the concentration of semi-volatile organic compounds. The system consisted of multiple capillary traps bundled together, providing high sample flow rates. The analytes were desorbed from the multi-capillary bundle and refocused in a secondary trap. The simultaneous focusing and separation effect of a trap subjected to a negative temperature gradient was also explored. In this configuration, analytes were focused because the front of the peak was at a lower temperature than the rear of the peak and, hence, moved slower. In addition to the focusing effect, analytes with different volatilities focused at different temperatures within the gradient, allowing for separation.

Methods for fast, simple detection of biomarkers to detect and differentiate closely related Bacillus endospores including Bacillus anthracis (BA), Bacillus thuringiensis (BT), Bacillus atrophaeus (BG), and Bacillus cereus (BC) using thermochemolysis and methylation (TCM), coiled wire filament (CWF), solid phase micro extraction (SPME) and gas chromatography-mass spectrometry (GC-MS) were developed. The main biomarkers detected and used for differentiation include dipicolinic acid methyl ester (DPAME), fatty acid methyl esters (FAMEs), 3-methyl-2-butenoic acid methyl ester (3M2BAME), 2-butenoic acid methyl ester (2BAME), and several methylated sugars. TCM of endospores was performed based on hydrolysis and methylation at elevated temperature after the endospores were mixed with sulfuric acid (H2SO4) with or without addition of tetramethylammonium hydroxide (TMAH) in methanol (MeOH). TCM products were then introduced into a heated GC injector port using a coiled wire filament (CWF) or solid phase microextraction (SPME) for detection and differentiation of the endospores by GC-MS.The CWF, which consisted of a tiny platinum helical wire coil attached to a retractable plunger that moved the coil in and out of a syringe needle housing, allowed for sampling to be accomplished by dipping the CWF in an endospore sample suspension, evaporating the suspension liquid, and then introducing the CWF into the injection port to enable on-line TCM. New SPME techniques, including half-half extraction, coated-needle extraction (CNE), and a new home-made polymer coated needle were used to speed up solid phase micro extraction of biomarkers produced from TCM. These simplified the detection of anthrose and other biomarkers. TCM with a CWF and TCM with SPME produced high intensity profiles of DPAME, FAMEs, 2BAME, 3M2BAME and methylated sugars. While the presence of DPAME can be used for the general detection of endospores (Bacillus and Clostridium) and the presence of 3M2BAME for the detection of BA, specific saturated and unsaturated C15, C16, and C17 fatty acid methyl esters and methylated sugars provide additional information for differentiating various Bacillus species grown at different temperatures and in different media. DPAME was detected in samples containing as few as 2,500 and 6,000 endospores using TCM-CWF with and without a concentration step, respectively. GC-MS peak area percent reproducibility for FAMEs using TCM and CWF varied from 3 to 13% (RSD). Better than 97% correct predictability of Bacillus species identity was obtained from a blind experiment consisting of 145 samples using DPAME and specific FAMEs. Conventional SPME and a modified form of "in-needle" extraction allow for detection of the biomarkers in less than 35 min. The detection limits with SPME sample introduction injection were approximately 5 x 103 endospores.Using these approaches, differentiation of Bacillus endospores and other biological agents grown under different conditions were based on the following characteristics: (1) presence of DPAME and specific FAMEs (iso or anteiso C15:0 and iso or anteiso C17:0) in Bacillus endospores, (2) unique presence of 3M2BAME (anthrose by-product) in BA, (3) absence of 2-butenoic acid methyl ester in BG, and (4) presence and absence of specific methylated monosaccharides in various Bacillus species. Clostridium endospores and non-sporulating bacteria, such as Yersinia pestis (YP) and Francisella tularensis (FT) could also be easily distinguished from Bacillus endospores based on the presence and absence of several specific sugar derivatives and fatty acid methyl esters (FAMEs), such as iso or anteiso C15:0 and iso or anteiso C17:0, and > C18 FAMEs which were simultaneously produced during TCM.

This dissertation focuses on the development of analytical methodology for the analysis of polycyclic aromatic hydrocarbons (PAHs) in water samples. Chemical analysis of PAHs is of great environmental and toxicological importance. Many of them are highly suspect as etiological agents in human cancer. Among the hundreds of PAHs present in the environment, the U.S. Environmental Protection Agency (EPA) lists sixteen as "Consent Decree" priority pollutants. Their routine monitoring in environmental samples is recommended to prevent human contamination risks. A primary route of human exposure to PAHs is the ingestion of contaminated water. The rather low PAH concentrations in water samples make the analysis of the sixteen priority pollutants particularly challenging. Current EPA methodology follows the classical pattern of sample extraction and chromatographic analysis. The method of choice for PAHs extraction and pre-concentration is solid-phase extraction (SPE). PAHs determination is carried out via high-performance liquid chromatography (HPLC) or gas chromatography/mass spectrometry (GC/MS). When HPLC is applied to highly complex samples, EPA recommends the use of GC/MS to verify compound identification and to check peak-purity of HPLC fractions. Although EPA methodology provides reliable data, the routine monitoring of numerous samples via fast, cost effective and environmentally friendly methods remains an analytical challenge. Typically, 1 L of water is processed through the SPE device in approximately 1 h. The rather large water volume and long sample processing time are recommended to reach detectable concentrations and quantitative removal of PAHs from water samples. Chromatographic elution times of 30 - 60 min are typical and standards must be run periodically to verify retention times. If concentrations of targeted PAHs are found to lie outside the detector's response range, the sample must be diluted (or concentrated), and the process repeated. In order to prevent environmental risks and human contamination, the routine monitoring of the sixteen EPA-PAHs is not sufficient anymore. Recent toxicological studies attribute a significant portion of the biological activity of PAH contaminated samples to the presence of high molecular weight (HMW) PAHs, i.e. PAHs with MW ≥ 300. Because the carcinogenic properties of HMW-PAHs differ significantly from isomer to isomer, it is of paramount importance to determine the most toxic isomers even if they are present at much lower concentrations than their less toxic isomers. Unfortunately, established methodology cannot always meet the challenge of specifically analyzing HMW-PAHs at the low concentration levels of environmental samples. The main problems that confront classic methodology arise from the relatively low concentration levels and the large number of structural isomers with very similar elution times and similar, possibly even virtually identical, fragmentation patterns. This dissertation summarizes significant improvements on various fronts. Its first original component deals with the unambiguous determination of four HMW-PAHs via laser-excited time-resolved Shpol'skii spectroscopy (LETRSS) without previous chromatographic separation. The second original component is the improvement of a relatively new PAH extraction method - solid-phase nanoextraction (SPNE) - which uses gold nanoparticles as extracting material for PAHs. The advantages of the improved SPNE procedure are demonstrated for the analysis of EPA-PAHs and HMW-PAHs in water samples via GC/MS and LETRSS, respectively.

Microalgae hold much promise as a feedstock in liquid biofuel production. Lipid content of microalgae cells range from 30-80% dry weight of biomass. It is projected that microalgae can produce between 1,000-6,500 gallons/acre/year of oil. Currently, production of industrial algae operates in open raceway ponds that use minimal capital and energy inputs to culture algae. Raceway ponds can also be used to grow microalgae from municipal waste streams. Although high biomass productivity can be achieved in these systems, there remains a large production gap between large volumes of biomass cultivation and high lipid content from microalgae cells. Low lipid content has been ameliorated through laboratory manipulations of nitrogen availability and light intensity. This two-part project measured microalgae lipid levels in open raceway ponds located at the San Luis Obispo Water Reclamation Facility (SLO WRF) grown in primary clarifier effluent and then performed nitrogen depletion and light-shift methods on cultures to increase triglyceride (TAG) content. The raceway ponds reached maximum biomass productivity of 24 g/m2-day, but with minimal TAG reserves. Optimization of both biomass productivity and TAG content can be achieved in April and September with 13 g/m2-day productivity and 13% TAG content. Investigation of increased TAG production responses were performed on wastewater microalgae (predominately Scenedesmus sp.) through N-depletion and three light treatments: light-shift on day 3 (before N-depletion), light-shift on day 5 (near N-depletion), and a double-illumination treatment. Highest levels of TAG content were observed in the double-illumination treatment and reached a maximum of 49% TAG in 9 days.

The focus of this study was analytical investigations of Egyptian paintings, mainly Coptic icons and Islamic wooden ceilings, dating from 1300-1900 using multiinstrumental techniques. Twenty three Coptic icons and three wooden ceilings dated from different periods and painted by different painters in case of icons were examined. The materials used including pigments, media, varnishes, ground layers and gold layers. The surface stratigraphy of paint samples, their layered structured and the composition of materials used in each layer were analysed. Variations in painting techniques, pigments palettes, paint media and varnishes applied in Egyptian paintings according to painters, time and type of paintings were revealed. A total of twenty-eight organic and inorganic pigments were identified in this study, of which nine have never been previously included as a part of the Egyptian pigment palettes, namely; smalt, lapis lazuli, indigo, pararealgar, Prussian blue, chrome yellow, barium yellow, barium white and hydromagnesite. The identification of hydromagnesite, which has never been to date considered as a pigment either in Egypt or elsewhere and the identification of smalt from the mid-14th century, whose reported earliest large scale use was in the 16th century. Two types of resins were identified as a constituent of the oil/resin varnish applied on Coptic icons of which Venice turpentine has been identified for the first time as an ingredient of Egyptian varnishes. The identification of mosaic gold in an 18th C. icon, a novel usage of dammar resin and the multilayered structure of the white ground layers were revealed. / Egyptian Ministry of Higher Educations