Current commercially available mimics contain varying amounts of either the actual explosive/drug or the chemical compound of suspected interest by biological detectors. As a result, there is significant interest in determining the dominant chemical odor signatures of the mimics, often referred to as pseudos, particularly when compared to the genuine contraband material. This dissertation discusses results obtained from the analysis of drug and explosive headspace related to the odor profiles as recognized by trained detection canines. Analysis was performed through the use of headspace solid phase microextraction in conjunction with gas chromatography mass spectrometry (HS-SPME-GC-MS). Upon determination of specific odors, field trials were held using a combination of the target odors with COMPS. Piperonal was shown to be a dominant odor compound in the headspace of some ecstasy samples and a recognizable odor mimic by trained detection canines. It was also shown that detection canines could be imprinted on piperonal COMPS and correctly identify ecstasy samples at a threshold level of approximately 100ng/s. Isosafrole and/or MDP-2-POH show potential as training aid mimics for non-piperonal based MDMA. Acetic acid was shown to be dominant in the headspace of heroin samples and verified as a dominant odor in commercial vinegar samples; however, no common, secondary compound was detected in the headspace of either. Because of the similarities detected within respective explosive classes, several compounds were chosen for explosive mimics. A single based smokeless powder with a detectable level of 2,4-dinitrotoluene, a double based smokeless powder with a detectable level of nitroglycerine, 2-ethyl-1-hexanol, DMNB, ethyl centralite and diphenylamine were shown to be accurate mimics for TNT-based explosives, NG-based explosives, plastic explosives, tagged explosives, and smokeless powders, respectively. The combination of these six odors represents a comprehensive explosive odor kit with positive results for imprint on detection canines. As a proof of concept, the chemical compound PFTBA showed promise as a possible universal, non-target odor compound for comparison and calibration of detection canines and instrumentation. In a comparison study of shape versus vibration odor theory, the detection of d-methyl benzoate and methyl benzoate was explored using canine detectors. While results did not overwhelmingly substantiate either theory, shape odor theory provides a better explanation of the canine and human subject responses.

Orientadora: Profa. Dra. Ivanise Gaubeur / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Ciência e Tecnologia/Química, Santo André, 2018. / Este trabalho teve como objetivo o desenvolvimento de metodos analiticos por espectrofotometria UV-Vis e voltametria de onda quadrada apos a microextracao em fase liquida, para a determinacao de aluminio complexando com quercetina e extraindo com 1-butanol e carbendazim (CBZ) extraido com oleo de soja. Estes solventes extratores foram utilizados ineditamente para a micro-extracao em fase liquida (LPME) e os parametros que influenciam na determinacao de aluminio, como quantidade de quercetina e volume de solvente extrator foram avaliadas de maneira univariada. Para carbendazim foi avaliada a formacao de emulsao com TBAC para melhoria da frequencia analitica. Foram estimadas as caracteristicas analiticas do metodo proposto: para Al: faixa linear de 8 . 165 ¿Êg L-1, LOD de 2 ¿Êg L-1 e LOQ de 7 ¿Êg L-1 e para CBZ: faixa linear de 1,0 . 19,1 mg L-1, LOD de 0,5 mg L-1 e LOQ de 1,6 ¿Êg L-1. Foi avaliada a exatidao do procedimento para aluminio aplicando o metodo proposto em material de referencia certificado de agua (NIST SRM 1643e) e farinha de arroz (NIST SRM . 1568c) e obtiveram-se resultados concordantes em um intervalo de confianca de 95%. Para carbendazim a viabilidade do metodo proposto foi feita com a adicao e recuperacao em amostras de sucos citricos e agua de lavoura obtendo valores variando de 88 - 121%. / This work developed a liquid phase microextraction (LPME) analytical methods for determination of aluminum complexing with quercetin and extracting with 1-butanol and determination of carbendazim (CBZ) extracted with soybean oil analyzed by UV-Vis spectrophotometry and square wave voltammetry, respectively. These extractants solvents were never used for LPME and the parameters that influence the determination of aluminum as amount of quercetin and volume of solvent extractor were evaluated in a univariate way. For CBZ the emulsion with TBAC was evaluated for analytical frequency improvement. The analytical features of the proposed method were estimated Al: linear range of 8 - 165 ìg L-1, LOD of 2 ìg L-1 and LOQ of 7 ìg L-1 and CBZ: linear range of 1.0 ¿ 19.1 mg L-1, LOD of 0.5 mg L-1 and LOQ of 1.6 mg L-1. The accuracy of the procedure for aluminum was evaluated by applying the proposed method in certified water reference material (NIST SRM 1643e) and rice flour (NIST SRM - 1568c) and obtained concordant results in a 95% confidence interval. For carbendazim the viability of the proposed method was evaluated by recovery percentage range in samples of citrus juices and crop water obtaining values from 88 - 121%.

Orientador: Fabio Augusto / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T10:01:00Z (GMT). No. of bitstreams: 1 Sampaio_BrunaReginadeToledo_M.pdf: 17858649 bytes, checksum: c23714f1f5bd4e3d6e831f6705306053 (MD5) Previous issue date: 2015 / Resumo: Nesta dissertação é descrita duas novas abordagens para microextração em fase sólida. A primeira delas tem como objetivo aumentar a massa extraída já que a mesma é limitada pelo reduzido volume da fase extratora. Para isso, foi proposto o desenvolvimento de um dispositivo, no qual ocorre a compartimentalização do processo de dessorção dos analitos da matriz e a sorção dos mesmos pela fibra de SPME. Dessa forma é possível operar simultaneamente nas temperaturas ótimas de cada processo. O processo de extração ocorre no modo headspace dinâmico, no qual um gás de purga é percolado pela matriz, tornando-se saturado pelos analitos. Este gás transporta os analitos para o interior do dispositivo onde os mesmos serão extraídos pela fibra de SPME resfriada. Esse resfriamento é necessário pois a sorção do analitos pela fibra é um processo exotérmico. Já a segunda abordagem propõe a confecção de novas fibras sortivas baseadas em polímeros iônicos líquidos com o intuito de expandir a aplicabilidade da SPME pois comercialmente, a quantidade de fibras disponíveis é bastante limitada, principalmente no que se refere à extração de analitos polares. Nesta abordagem foi possível a criação de uma nova rota para confecção de fibras baseadas em polímeros iônicos líquidos empregando-se nitinol como suporte, o que promoveu maior resistência e durabilidade para a fibra. Estas novas fibras apresentaram precisões com valores de desvio padrão relativo em torno de 15% e robustez em condições severas de extração; tais fibras foram aplicadas, para prova de conceito, em um estudo de detecção e quantificação de adulteração em café / Abstract: This thesis describes two new approaches to solid-phase microextraction (SPME). The first aims to increase the extracted mass since, which is limited by the small volume of the extraction phase. In this context, it is proposed the development of a device that compartmentalizes the desorption of the analytes from the matrix to the headspace and their sorption by the SPME fiber. This setup allows the simultaneous operation of each process at their optimum temperatures. The extraction process takes place in the dynamic headspace where a inert purge gas is percolated through sample matrix, becoming saturated with the analytes. This gas, then, transports the analytes to the device where they will be sorbet by cold SPME fiber. This cooling is necessary since the sorption of analytes by the fiber is an exothermic process. The second approach proposes the development of new sorbent coatings based on polymeric ionic liquids. It was possible to create a new route for manufacturing nitinol-based SPME fibers coated with PIL providing greater strength and durability of the fiber. These new fibers showed precision with relative standard deviations below 15% and robustness in harsh conditions of extraction / Mestrado / Quimica Analitica / Mestre em Química

This thesis is focused on aroma compounds which are presented in a wide variety of products including perfume, cologne, cosmetics, toiletries, laundry products and detergens. The widespread use and exposure to aroma compounds of aforementioned products could cause a range of the adverse reactions such as contact dermatitis, asthma, eczema and breathing problems. There are a lot of aroma compounds triggering negative allergic reactions but EU regulations limit 26 the most important fragrance allergens. The presence of these substances has to be declared on the product label if a limit of 0,01 % for rinse off and 0,001 % for leave-on products is exceeded. Of these 26 substances, a methodology was elaborated for determination of 12 allergens in a experimental part of this thesis. A method by solid-phase microextraction (SPME) and gas chromatography-flame ionization detection (GC-FID) was applied for fragrance allergens identification, extraction and measurement. The optimal extraction conditions of SPME-GC method were investigated including equilibrium time, extraction time and extraction temperature to increase extraction efficiency. Another important point is the method by SPME-GC-FID was validated and following performance parameters were determined: repeatability, linearity, limit of detection (LOD) limit of quantitation (LOQ). SPME-GC-FID was tested and applied to real samples.

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.

Fragrances are added to food, cosmetics and other products primarily for enhancement of their sensory quality (taste and/or aroma). However, the usage of these compounds is associated with the wide range of various adverse biological effects. Some fragrances widely used in cosmetics are proved to cause e.g. skin sensitization, rashes, dermatitis, headache, cough etc. To protect the health of consumers, European union approved the cosmetic directive (ES/1223/2009) that requires the labeling of 26 allergen fragrances on the final product label, if concentration exceeds the given level (0,01 % for rinse-off and 0,001 % for leave-on product). However, some producers hide the presence of allergens in the final product under the general term „aroma“. For this reason it is very important to monitor the content of these substances in cosmetic products. Fragrances are found not only in cosmetics, but the various types of food are also aromatized by them. Unlike cosmetics, the food producers are not obliged to label the presence of fragrance allergens on the packaging. Therefore, the monitoring of these fragrances is highly desirable because of the potential health risks they pose. The aim of this study was to develop a method for simultaneous determination of regulated fragrance allergens in food and everyday use products. The method based on extraction of analytes by solid phase microextraction coupled to gas chromatography with FID detection (HS-SPME-GC-FID) was chosen on the basis of the literature review. The fiber CAR/PDMS provided the highest extraction efficiency among the SPME fibers tested. Univariate and multivariate data analysis were used to optimize the main parameters affecting microextraction process. The final method validation was performed in terms of linearity, repeatability, reproducibility, recovery, limits of detection and quantification. The optimized and validated method was applied to a wide range of products including cosmetics, aromatized food and fragranced toys. These products were also subjected to sensory evaluation especially in terms of taste and/or aroma (i.e. flavour), which may be associated with the content of the monitored fragrances. The profile test (EN ISO 13299) and seven-point category ordinal scale (ISO 4121) were used for sensory evaluation.

The aim of the presented Diploma Thesis was to develop a new method for the indirect determination of formaldehyde in wood-based products using gas-diffusion microextraction coupled with electrochemical detection on unmodified screen-printed electrodes (MLEM-SPCE). Formaldehyde released from the sample is derivatized using an acetylacetone reagent present in an acceptor solution. The product of derivatization of formaldehyde with acetylacetone is 3,5-diacetyl-1,4-dihydrolutidine (DDL) which forms a selective oxidation voltammetric peak at a potential of 0.4 V. Detection and quantification limits of 0.57 mg kg−1 and 1.89 mg kg−1 , respectively, were obtained, together with intra- and inter-day precision below 10% (as relative standard deviation, RSD). The developed methodology was applied to determine formaldehyde content in seven samples. Similar results were obtained from the European standard method EN 717-3 with a significant reduction of total analysis time. The developed method MLEM-SPCE, which combines the use of a new sample preparation procedure for volatile compounds with the firstly introduced determination of formaldehyde (as the derivative product DDL) on unmodified SPCEs, proves to be a promising alternative for the determination of formaldehyde in wood-based products and other samples.

The purpose of this thesis work was to develop a headspace solid phase microextraction gas chromatography mass spectrometry (HS-SPME-GC-MS) method to detect volatile organic compounds (VOCs) in board samples and to statistically investigate potential correlation between chromatographic data and flavor data obtained from a trained panel. The developed method would hopefully serve as a complement to the already established routine analyses at Stora Enso and gain an increased understanding of which VOCs in the board influence its flavor properties. The impact of incubation time and adsorption time on the area under curve (AUC) was studied with a Design of Experiment screening using the software MODDE. The screening data showed a correlation between large AUC and low repeatability measured as relative standard deviation (RSD). The data was hard to fit to a model due to the large RSD values for the replicates, AUC for identified compounds as response gave an acceptable fit. The regression coefficients for the model showed that a longer adsorption time gave larger AUC, while incubation time had no significant impact on the response.  Instead of following up the screening with an optimization, the focus was shifted to improving the repeatability of the method, i.e. lowering the RSD. The high RSD was believed to mainly be the result of leakage of analytes and unstable temperature during adsorption, preventing the system from reaching equilibrium. Different heating options and capping options for the vial was tested. Septum in crimp cap ensured a gas tight seal for the vial, giving lower RSD values and larger AUC compared to the other alternatives, showing that there was indeed a leakage. Using oil bath ensured stable temperature during the adsorption and detection of a larger number of VOCs but created a temperature gradient in the vial due to it not being fully submerged in the oil. Oil bath gave larger AUC, but still high RSD due to the temperature gradient making the method sensitive to variance in fiber depth in the vial. The final method was performed with 2 g of board sample in a 20 ml headspace vial sealed with a crimp cap with septa. The incubation and adsorption were performed with the vial immersed in a 90-degree oil bath. 20 min incubation time was chosen based on the time it took to get a stable temperature gradient in the vial, and 20 minutes adsorption time was chosen as a good compromise between large AUC and low RSD. Compared to Stora Ensos routine analysis, the developed SPME method gave chromatograms with an improved signal-to-noise ratio for the base line and several more peaks with larger AUC. For the board sample used during method development, the SPME-method identified 34 VOCs, while the routine analysis only identified 12. The developed method was applied on 11 archived board samples of the same quality that were selected based on their original flavor properties, to get a large diversity of samples. Flavor analysis was performed by letting a trained flavor panel describe the flavor based on intensity and character of the water that had individually been in indirect contact with one of the 11 board sample for 24 h. Potential correlation between chromatographic data obtained with the developed method and the flavor experience described by the flavor panelists was statistically investigated with the multivariate analysis software SIMCA. The correlation study showed that a combination of 12 VOCs with short retention time are most likely the main source of off-flavor which of 5 could only be identified with the developed SPME method. VOCs with long retention time did not contribute to an off-flavor and might have a masking effect on flavor given by other VOCS, however not confirmed in this study. Furthermore, the age of the board samples proved to be a good indicator for prediction of the flavor intensity, whereas the total AUC of the samples was not. Possible correlation between detected VOCs in the samples and flavor character given by the flavor panel were seen, however the variation in the data and the sample set were too small, preventing from making conclusions on individual VOCs impact on the flavor experience. The developed HS-SPME-GC-MS method would serve as a complement to the already established routine analyses at Stora Enso and has slightly increased the understanding of which VOCs in the board influence the flavor properties

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.

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.