No / RATIONALE: The carbon isotopic characterisation of ruminant lipids associated with ceramic vessels has been crucial for elucidating the origins and changing nature of pastoral economies. delta(13)C values of fatty acids extracted from potsherds are commonly compared with those from the dairy and carcass fats of modern domesticated animals to determine vessel use. However, the processing of wild ruminant products in pottery, such as deer, is rarely considered despite the presence of several different species on many prehistoric sites. To address this issue, the carbon isotope range of fatty acids from a number of red deer (Cervus elaphus) tissues, a species commonly encountered in the European archaeological record, was investigated. METHODS: Lipids were extracted from 10 modern red deer tissues obtained from the Slowinski National Park (Poland). Fatty acids were fractionated, methylated and analysed by gas chromatography/combustion/isotope ratio mass spectrometry (GCCIRMS). The delta(13)C values of n-octadecanoic acid and n-hexadecanoic acid, and the difference between these values (Delta(13)C), were compared with those from previously published ruminant fats. RESULTS: Nine of the ten deer carcass fats measured have Delta(13)C values of less than -3.3 per thousand, the threshold previously used for classifying dairy products. Despite considerable overlap, dairy fats from domesticated ruminants with Delta(13)C values less than -4.3 per thousand are still distinguishable. CONCLUSIONS: The finding has implications for evaluating pottery use and early pastoralism. The processing of deer tissues and our revised criteria should be considered, especially where there is other archaeological evidence for their consumption.

Yes / Red Lustrous Wheelmade ware is one of the most recognisable classes of pottery from the Late Bronze Age of the east Mediterranean. Yet both its production source and the nature of its contents and use remain a source of some debate. These questions are tackled here through an intensive programme of scientific analysis involving 95 samples of Red Lustrous Wheelmade ware and related wares from seven sites in Turkey, Cyprus and Egypt. Petrography and instrumental neutron activation analysis are combined in the study of the ceramic fabrics, with a view to specifying the source of this ware; while gas chromatography and gas chromatography-mass spectrometry are used to analyse absorbed and visible residues in and on the sherd samples, in the hope of shedding light on vessel contents and possible use. The results of the fabric analysis show the ware to be extremely homogeneous, indicative of a single source: northern Cyprus is at present the most likely candidate, although further analysis, particularly of clay samples from the region in question, would certainly be desirable. The residue analysis suggests that Red Lustrous Wheelmade ware might have been used to carry some kind of plant oils, possibly perfumed, and that in some instances the vessel interior was coated with beeswax as a sealant. / AHRC

No / During the micro-excavation of the cauldrons, residues were identified which appeared different from the surrounding soil and metal corrosion products. Thirty-seven of these residues from nine cauldrons and two significant fragments of incomplete cauldrons were analysed by gas chromatography-mass spectrometry (GC-MS) along with two samples of soil from the micro-excavation for comparison. The aim of the analysis was to determine whether these residues contained any organic material related to the use of the cauldrons, specifically lipids (fats, waxes, resins etc.) from the preparation of food or drink. Two of the samples from the cauldrons were also sent for compound specific carbon stable isotope analysis by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) to give a more precise identification of the residues.

Yes / Transport and storage vessels in Red Lustrous Wheelmade ware (RLWm ware) were traded across a large area of the eastern Mediterranean for approximately 300 years (c. 1500–1200 BCE) during the Late Bronze Age (c.1600–1000 BCE). The extreme consistency of the ceramic, in form, fabric, chemistry and mineralogy, points to a single production source for the ware, which, although no kiln sites have been identified, is generally accepted to have been on Cyprus. The aim of this study was to determine whether organic residues were present in this very fine, dense ware, and to characterise the contents of RLWm ware vessels from different sites, contexts and periods, and of different forms, to improve our understanding of the trade in this ceramic type. To that end, 101 RLWm ware sherds, together with three visible residues, were examined from sites in Turkey, Cyprus, Egypt and Syria. Residues were identified in more than half of the samples, indicating that organic material is absorbed into and preserved in this very fine fabric. Four commodities were identified: fat (probably plant oil), which in four residues was identified further as castor oil; beeswax; bitumen; and Pinaceae spp. resin. The commodities were found alone or, occasionally, one of the latter three was combined with the fat or oil. Fatty material was the only commodity present at all sites and its wide distribution may indicate that generally the vessels were used for a mixture or mixtures based on plant oils, in some cases containing castor oil. It was impossible to determine whether the beeswax, bitumen and resin formed part of this mixture or represented post-firing treatments of the ceramic to make it less porous. The identification of more than one type of residue indicates that RLWm ware vessels did not always contain the same commodity. No significant correlation could be detected between the vessel forms, and the dating of many of the sherds was not precise enough to reveal any variation through time. The type of residue present did vary depending on the geographical location of its final use. Beeswax was, with two exceptions, only present in samples from Turkey, while bitumen was found exclusively in samples from Cypriot sites. The occurrence of at least one example of every commodity in the samples from Cyprus is consistent with the theory that this ware was manufactured on Cyprus, and indicates that the vessels could also have been filled and exported from there. The variation in content of the vessels found in different geographical areas could highlight a special trading relationship between the Hittite heartland in Turkey and the Cypriot potters who produced the ware, and a possible trade in bitumen as a raw material between the north Syrian coastal area of Ugarit and Cyprus. / This research was funded by an AHRC PhD studentship (number 110786), awarded to V. Steele.

<p>Određivanje koncentracije etanola u telesnim tečnostima, pre svega u krvi, neophodan je uslov da bi se ustanovio uticaj alkoholemije na psihomotorne sposobnosti. Poznavanje stabilnosti lekova, droga i metabolita u biolo&scaron;kim uzorcima je od ključne važnosti kada se ukaže potreba za ponovljenom analizom i evaluacijom rezultata u sudskom postupku. Osnovni ciljevi ovog rada su da se uz pomoć HS-GC metode (hedspejs gasna hromatografija) ustanovi da li postoji statistički značajna promena koncentracije etanola u uzorcima krvi dobijenih od živih osoba i u biolo&scaron;kim uzorcima uzorcima sa autopsijskog materijala. Na osnovu rezultata potrebno je bilo utvrditi u kojem tipu uzorka uzetog sa le&scaron;nog materijala postoji najmanja promena koncentracije tokom perioda čuvanja uzorka. Istraživanje je bilo otvoreno, randomizirano i prospektivnog tipa. Biolo&scaron;ki uzorci krvi krvi živih osoba i le&scaron;nog materijala (krv, mokraća i staklasto telo) uzimani su metodom slučajnog izbora, u rasponu alkoholemije od 0,1 mg/ml do 5 mg/ml. Nakon inicijalne dvostruke analize, jedan biolo&scaron;ki uzorak čuvan je u trajanju od 180 dana, dok je drugi otvaran i analiziran nakon 60, 120 i 180 dana. Ukupan broj analiza alkoholemije u krvi živih osoba iznosio je 500. Ukupan broj analiza koncentracije etanola u krvi, mokraći i staklastom telu sa le&scaron;eva iznosio je 360. Etanol je u uzorcima krvi živih osoba, kao i u biolo&scaron;kim uzorcima sa autopsijskog materijala određivan metodom HS GC. Tokom čuvanja biolo&scaron;kih uzoraka u periodu od &scaron;est meseci ustanovljeno je da je do&scaron;lo do značajnog smanjenja koncentracije etanola u svim analiziranim uzorcima, nezavisno od njegovog porekla. Promena koncentracije etanola tokom čuvanja u zavisnosti je od tkivne vrste uzorka, inicijalne alkoholemije, dužine čuvanja, integriteta vijala i čepova, temperature, odnosa tečne i gasne faze, prisustva konzervansa i potencijalnog intermitentnog otvaranja radi analiza.</p> / <p>Determination of ethanol concentration in body fluids, especially blood, is a necessary objective to establish the influence of alcohol on psychomotor skills. Knowing the stability of medicines, drugs and metabolites in biological samples is of crucial importance when there is a need for repeated analysis and result evaluation in court. The main objectives of this work were to determine whether there was a statistically significant change in ethanol concentration in blood samples obtained from living subjects and from autopsy material, by using HS-GC method (headspace gas chromatography). Based on the results it was necessary to determine which type of sample collected from autopsy showed the lowest change in concentration during the storage period. The study was open, randomized and prospective. Biological samples of living person&#39;s blood and autopsy biological samples (blood, urine and the vitreous humor) were taken at random, in the level range between 0.1 mg/ml and 5 mg/ml. After an initial duplicate analysis, one biological sample was stored for a period of 180 days, while the other was opened and analyzed after 60, 120 and 180 days. Total number of analysis of living person&#39;s blood samples was 500. The total number of analysis of autopsy biological samples was 360. All concentrations were determined by HS-GC method. During the storage, results showed that there has been a significant decrease in the concentration of ethanol in all of the analyzed samples, regardless of its origin. The level of this change was dependent on the type of tissue sample, initial alcohol concentration, duration of storage, integrity of the vials and stoppers, temperature, ratio of liquid and gas phases, presence of preservatives and intermittent opening for analysis.</p>

Red Lustrous Wheelmade Ware (RLWm ware) transport and storage vessels have been excavated from Late Bronze Age (LBA) sites across the eastern Mediterranean. These distinctive vessels were traded for the valuable commodity they contained so far unidentified. Seventy-three sherds (61 RLWm ware, 12 in local fabrics) and two visible residues were analysed for organic residues using standard lipid extraction techniques. Seven residues from a previous study were re-examined. Gas chromatography-mass spectrometry identified four materials - beeswax, bitumen, fat/oil and resin. Beeswax, found only in vessels from Hittite sites in Turkey, was probably used as a post-firing treatment. Fat/oil, present in some sherds from every site, represents the contents of the vessels and showed many of the characteristics of degraded plant oil. Two examples contained a plant sterol and three yielded ricinoleic acid, a biomarker for castor oil. Gas-chromatography compound-specific isotope ratio mass spectrometry of selected residues excluded dairy products, ruminant animal fats and fish oils as source materials for the fats/oils, while comparison with a small database of modern oils created during this study does not exclude plant oils. Selected samples analysed by high performance liquid chromatography-tandem mass spectrometry did not reveal wine residues. Data on the elemental composition of the fabric collected during another study was re-analysed and compared with data from a further published study, confirming the remarkable consistency of RLWm ware fabric. Volume calculations were also attempted to give an estimate of the capacity of the main vessel forms.

O estado de São Paulo é responsável por 70% da produção nacional de flores e plantas ornamentais. Esses cultivos ocupam 7,5 mil hectares e mais da metade desta área é cultivada em estufas. Atualmente existem aproximadamente 8 mil produtores de pequeno, médio e grande porte em todo Brasil e este setor gera em torno de 200 mil empregos diretos, abrangendo produção e comércio. As estufas são microcosmos planejados para propiciar as condições ambientais adequadas ao crescimento de plantas. Qualquer infestação é controlada usando praguicidas que, devido ao enclausuramento e ajustes das condições climáticas, podem prolongar e intensificar a exposição ocupacional aos mesmos. Alguns estudos sugerem que os trabalhadores de estufas de flores e plantas ornamentais estão expostos a níveis mais elevados de praguicidas durante o carregamento, mistura e aplicação dos praguicidas, bem como pelo contato contínuo com as flores e plantas ornamentais, quando comparados a outros trabalhadores que entram em contato com essa classe de compostos. No presente trabalho, objetivou-se conhecer o processo de trabalho, práticas de saúde, higiene e segurança e localizar possíveis fontes de exposição ocupacional a praguicidas nas estufas de flores da região do Alto Tietê, e também otimizar métodos analíticos para a detecção e quantificação de praguicidas organofosforados (diclorvós, metil-paration e metidation) em patches de algodão e em tubos coletores XAD-2, com o intuito de analisar a exposição ocupacional dérmica e inalatória. O processo de avaliação incluiu o acompanhamento da jornada de trabalho, entrevistas e aplicação de questionários de trabalhadores de 18 estufas. Destas 18 foram selecionadas 6 estufas para coleta de amostras. Os organofosforados diclorvós, metidation e metilparation foram detectados e quantificados por cromatografia gasosa/espectrometria de massas (GC-MS), operado no modo de ionização por impacto de elétrons. Os dados da avaliação qualitativa demonstraram percentual elevado de desconhecimento das práticas adequadas de saúde, higiene e segurança para a utilização destes compostos, sugerindo que há risco de exposição durante a manipulação, armazenamento e descarte dos mesmos. Os limites de quantificação (LQ) obtidos foram abaixo de 0,4 ng/mL e limites de detecção (LD) foram abaixo de 0,1 ng/mL para todos os compostos. O método mostrou boa linearidade na concentração estudada (LSQ-500 ng/mL), com coeficiente (r) maior que 0,99. A precisão foi avaliada pelo desvio padrão relativo e apresentou valores inferiores a 15% para todos os compostos estudados. Após os métodos serem validados, foi realizada a amostragem dérmica e do ar e encontraram-se concentrações variadas de praguicidas. / The state of São Paulo - Brazil, accounts for 70% of domestic production of flowers and ornamental plants. Currently, these crops occupy 7.5 thousand hectares and over 50% of this area is cultivated in greenhouses. This market has an average of 8.000 producers and generates around 200.000 jobs. Greenhouses are microcosms designed to provide environmental conditions suitable for plant growth. Infestation is controlled using pesticides that due to the closure and adjustment to the weather conditions can prolong and intensify the exposure to them. Some studies suggest that workers in greenhouses of flowers and ornamental plants are exposed to higher levels of pesticides during loading, dilution and application, as well as by continuous contact with flowers and ornamental plants, when compared to other workers who enter in contact with this class of compounds. The aim of the present was to know the work process, to survey the practices of health, hygiene and safety standards and locate possible sources of occupational exposure to pesticides in greenhouses of flowers in the Alto Tietê region (São Paulo state), and to optimize analytical methods for detection and quantification of organophosphate pesticides (dichlorvos, methyl parathion and methidathion) in patches of cotton and in XAD-2 sorbent tubes, with the aim of analyzing the occupational dermal and inhalation exposure. The evaluation process included the monitoring of the working day, interviews and questionnaires, and samples collected in greenhouses. The organophosphorus compounds were detected and quantified by gas chromatography/mass spectrometry (GC-MS) operated in electron impact ionization. The data show a high percentage of lack of appropriate health practices, hygiene and safety for pesticide use suggests that there is risk of exposure during handling, storage and disposal of them. The limits of quantification (LOQ) obtained were below 0.4 ng/mL and limits of detection (LOD) were below 0.1 ng/mL for all compounds. The method showed good linearity in the studied concentration (LOQ-500 ng/mL), with coefficient (r) greater than 0.99. The precision was evaluated by relative standard deviation and showed values below 15% for all compounds studied. After the methods are validated, the dermal and air sampling was performed and a great range of pesticide concentrations was found. So it is evident that this study is valuable for future analysis and guidance to workers about possible hazards and proper use for reducing exposure to these compounds.

O aleitamento materno está associado a benefícios de ordem nutricional, imunológica, afetiva, econômica e social. Grande parte das drogas lícitas e ilícitas consumidas pela lactante pode ser transferida para o leite, o que pode representar potenciais efeitos nocivos para a criança em curto e longo prazos. Embora o conhecimento a respeito de substâncias psicoativas durante a lactação venha sendo ampliado, ainda há poucas informações sobre as concentrações de substâncias excretadas por essa via e muitas dúvidas sobre os efeitos delas em crianças durante o período de amamentação. O leite materno é uma matriz não convencional que pode ser usada para avaliar a exposição de crianças a substâncias durante o aleitamento e sua principal vantagem é a coleta simples e não-invasiva. Contudo, a extração destas a partir do leite materno é um desafio analítico devido ao seu alto conteúdo lipídico e proteico, bem como a alteração na sua composição durante o período pós-parto. No presente trabalho, técnicas analíticas miniaturizadas foram desenvolvidas visando a detecção das substâncias psicoativas cocaína, cocaetileno, norcocaína, tetraidrocanabinol, canabinol, canabidiol em amostras de leite materno, utilizando cromatografia gasosa acoplada à espectrometria de massas (GC-MS). A microextração em fase líquida (LPME) foi aplicada para analitos de cocaína e a microextração em fase sólida (SPME) para canabinoides. Após o desenvolvimento e validação dos métodos, as análises foram aplicadas em amostras de leite coletadas no hospital municipal Dr. Arthur Ribeiro de Saboya (n=109). Além das técnicas terem se mostrado adequadas à extração e detecção dos analitos, confirmou-se a excreção de cocaína no leite materno em quantidades moderadas com resultado positivo para uma amostra (138 ng/mL). Bem como foi detectado tetraidrocanabinol nas concentrações de 20 ng/mL e 31 ng/mL em amostras de leite humano. / Maternal breastfeeding is related with nutritional, immunological, affective, economic, and social benefits. Most licit and illicit substances consumed by the nursing mother might be excreted in breast milk, which may cause potential harmful effects to the breastfed infant at short and long terms. Although the knowledge about the psychoactive substances during lactation is increasing, there is still few information on the levels in which these substances are excreted in breast milk and many questions about the possible effects of these substances in the infant during the nursing period still remain unanswered. Breast milk is an unconventional matrix that can be used to assess infant exposure to drugs, and its main advantage is its easy and non-invasive collection. However, the extraction of substances from breast milk is an analytical challenge because of its high protein and fat content and changing composition during the postpartum period. In this study, miniaturized analytical techniques will be carried out to determine psychoactive substances such as cocaine, cocaethylene, norcocaine, tetrahydrocannabinol, cannabinol, and cannabidiol in milk samples by using gas chromatography-mass spectrometry (GC-MS). Liquid-phase microextraction (LPME) was applied to cocaine analytes and solid-phase microextraction (SPME) was applied to cannabinoids. After the development and validation, the methods were applied in milk samples collected from municipal hospital Dr. Arthur Ribeiro de Saboya (n=109). These techniques have proved to be suitable for analyte extraction and detection. Cocaine excretion in breast milk has been confirmed given that one sample was positive to cocaine in moderate amounts (138 ng/mL), as well as, two samples could be confirmed positive to tetrahydrocannabinol at 20 ng/mL and 31 ng/mL.

O uso de técnicas miniaturizadas de preparo de amostra vem se tornando uma tendência cada vez mais crescente em química analítica. Dentre elas o MEPS (Microextraction by a Packed Sorbent) apresenta grande potencial por poder ser acoplado on-line, sem grandes modificações, à cromatografia gasosa e líquida, não necessitando de grande quantidade de tempo para análise e seu cartucho sorvente ser reutilizável. O uso de MEPS, foi mais explorado até o presente momento na análise de fármacos em fluídos biológicos; dessa forma existe um pequeno número de publicações que exploram o uso dessa técnica na determinação de agrotóxicos em matrizes de alimentos. Por esse motivo, o presente trabalho teve como objetivo a avaliação do uso dessa técnica na determinação de seis agrotóxicos utilizados no cultivo da cana-de-açúcar (tebutiurom, carbofurano, atrazina, metribuzim, ametrina e bifentrina) em amostras de garapa. Para o desenvolvimento desse estudo foram verificadas dentre as variáveis pH, força iônica, solvente de eluição e volume do solvente de eluição, quais poderiam afetar o desempenho da técnica em diferentes fases extratoras, empregando nessa etapa de otimização planejamento fatorial fracionário 24-1. As fases avaliadas foram C18 Chromabond e HLB Oasis, assim como sistemas comercialmente disponíveis com as fases C18, C8, SAX, SCX e SIL. Durante essa etapa foi realizado um estudo inicial do uso do grafeno como material sorvente em MEPS, considerando as propriedades que esse material apresenta para atuar como adsorvente em técnicas de preparo de amostra. Contudo, o uso do grafeno apresentou entupimento no cartucho de sorção, problema ainda em avaliação. A fase C18 Chromabond foi a que apresentou os melhores resultados, sendo a escolhida para otimização dos parâmetros envolvidos na etapa de extração por MEPS. Os parâmetros otimizados por planejamento fatorial 23 foram os ciclos de: aspiração da amostra, lavagem e eluição. O método desenvolvido foi validado baseado nos critérios exigidos pelo MAPA e apresentou seletividade, linearidade e os limites de quantificação variaram de 2-10 &mu;g/L. A recuperação foi adequada para todos os analitos (71,7-106,9%), assim como a precisão intra e inter-dia que apresentou coeficientes de variação (CV) menores que 16%. O método desenvolvido foi aplicado em quatro amostras reais de garapa de diferentes regiões. / The use of miniaturized techniques in sample preparation has becoming a growing trend in analytical chemistry. Among these techniques MEPS (Microextraction by a Packed Sorbent) presents a great potential affording on-line coupling, without much modification to gas and liquid chromatography systems, in addition it does not require large analyses time and the sorbent cartridge is reusable. MEPS utilization has been explored mainly for drugs analyses in biological fluids, existing limited number of publications that apply this technique for pesticides analyses in food sample matrix. For this reason the goal of present work was the evaluation of MEPS in the analyses of six pesticides used in sugarcane cultivation (tebuthiuron, carbofuran, atrazine, metribuzine, ametryn and bifenthrin) in sugarcane juice samples. During the method development several variables were evaluated including pH, ionic strength, elution solvent and solvent volume, to determine which ones could affect the technique perform in different sorbent phases. For this optimization step, fractional factorial design 24-1 was utilized. Phases evaluated included C18 Chromabond and HLB Oasis, and also commercially available system containg C18, C8, SAX, SCX e SIL. During this step, it was also carried out an initial study employing graphene in a MEPS system; Tanking into account the properties that this material presents to act as adsorbent in sample preparation techniques. However the graphene showed obstruction problems in the sorption cartridge, whose solution is under way. The phase C18 Chromabond showed better results, and was chosen to MEPS parameters optimization. MEPs parameters optimized by full factorial desing 23 were the following cycles: sample aspiration, washing and elution. The method, was validated based upon the MAPA requirements and showed good selectivity, linearity an quantifications limits ranging from 2-10 &mu;g/L. Recovery was satisfactory for all pesticides (71,7-106,9%), intra- and inter-day precision were satisfactory and showed coefficients of variation (CV) less than 16%. Hence, the developed method was applied to the analysis of four real samples of sugarcane juice obtained from different regions.

Os antidepressivos pertencem a uma importante classe de medicamentos investigados na toxicologia forense. Em casos de amostras provenientes de cadáveres, o intervalo entre o óbito e a obtenção da espécie biológica pode proporcionar a redistribuição postmortem destes fármacos. Com o objetivo de elucidar esse fenômeno, métodos analíticos foram desenvolvidos e aplicados utilizando sangue total (ST), humor vítreo (HV) e fígado. Para as amostras de ST e HV, o método de extração escolhido e validado foi a microextração em fase líquida (LPME) trifásica. Fibras ocas constituídas de polipropileno, com a extensão de 8 cm cada, foram tratadas com o solvente orgânico dodecano (fase orgânica), resultando em um membrana com permeabilidade seletiva. No lúmen destas fibras, adicionou-se ácido fórmico 0,1 mol/L (fase aceptora). Em frasco de fundo chato com 5 mL de capacidade, pipetou-se 3,5 mL de NaOH 0,1 mol/L (fase doadora) e 0,5 mL de ST ou HV. Ao término da extração, as amostras foram introduzidas no GC-MS, sem a necessidade de reações de derivatização. O estudo com ST contemplou os antidepressivos amitriptilina (AMI), nortriptilina (NTR), imipramina (IMI), desipramine (DES), clomipramina (CLO), desmetilclomipramina (DMC), fluoxetina (FLU) e norfluoxetina (NFL). Os limites de quantificação para estas substâncias ficaram inferiores aos níveis terapêuticos (20 ng/mL). As médias dos coeficientes de variação intradia e interdia foram, respectivamente, de 9,7 e 9,8%. As curvas de calibração apresentaram linearidade entre as concentrações de 20 até 1200 ng/mL. A validação do parâmetro integridade da diluição assegurou a mensuração de quantidades superiores ao limite apresentado na curva de calibração. O método foi aplicado em sete amostras reais postmortem e em apenas um caso foi observada uma diferença significativa (300%) entre os valores quantificados no ST periférico e central. Os antidepressivos tricíclicos AMI, NTR, IMI e DES foram avaliados no HV e o efeito matriz foi detectado para os dois últimos analitos. O método foi otimizado e validado utilizando solução salina adicionada de AMI e NTR. O limite de detecção igual a 5 ng/mL, foi obtido com a redução da voltagem da fonte de íons do espectrômetro de massa para 50 eV. Coeficientes de variação foram inferiores a 15%. Os procedimentos validados foram aplicados em seis amostras reais de HV. A relação encontrada entre os valores obtidos no ST periférico e HV foi de aproximadamente 0,1. A extração acelerada por solvente (ASE) e, posteriormente, a extração em fase sólida (SPE) foram as técnicas de separação dos analitos da matriz fígado. Ao término das citadas extrações, os antidepressivos foram analisados no GC-MS. Para esta matriz sólida, são necessários mais estudos, pois os valores encontrados nos ensaios analíticos estão em desacordo com as diretrizes utilizadas na validação dos métodos. / Antidepressants belong to an important class of drugs investigated in forensic toxicology. In cases of samples from corpses, the interval between death and obtaining the biological specimens can provide the postmortem redistribution of these drugs. Aiming to elucidate this phenomenon, analytical methods were developed and applied using whole blood (WB), vitreous humor (VH) and liver. For samples of WB and HV, the extraction method chosen and validated was the three-phase liquid phase microextraction (LPME). Hollow fibers consist of polypropylene, with a length of 8 cm each were treated with dodecane organic solvent (organic phase) resulting in a membrane with selective permeability. Into the lumen of these fibers was added formic acid 0.1 mol/ L (acceptor phase). In the vial containing 3.5 mL of NaOH 0.1 mol / L (donor phase) was spiked 0.5 ml of biological fluids (WB or VH). Subsequently, the samples were injected in GC-MS without derivatization reactions. The study of the ST included antidepressants amitriptyline (AMI), nortriptyline (NTR), imipramine (IMI), desipramine (DES), clomipramine (CLO), desmethylclomipramine (DMC), fluoxetine (FLU) and norfluoxetine (NFL). The quantification limits for these substances were below the therapeutic levels (20 ng / ml). The mean coefficients of variation and separate intradays were respectively 9.7 and 9.8%. The calibration curves showed linearity between concentrations of 20 to 1200 ng / mL. The validation of the integrity of the dilution parameter assured measurement higher than the limit shown in the calibration curve quantities. The method was applied to seven real postmortem samples and in one case a significant difference (300%) between the measured values in the peripheral and central ST was observed. The tricyclic antidepressants AMI, NTR, IMI and DES were evaluated in VH and the matrix effect was detected in the last two analytes. The method was optimized and validated using saline spiked AMI and NTR. The limit of detection (5 ng/ml) was obtained by reducing the voltage of the ion source of the mass spectrometer 50 eV. Coefficients of variation were below 15%. The procedures were validated in six real samples of HV. The relationship found between the values obtained in the peripheral ST and HV was approximately 0.1. Accelerated solvent extraction (ASE) and subsequently the solid phase extraction (SPE) were the techniques of separation of analytes liver matrix. At the end of the cited extractions, antidepressants were analyzed in GC-MS. To this solid tissue, further studies are needed, because the values found in the analytical tests were not in accordance with the guidelines used in the validation of the methods.