Forensic Geochemistry Reveals International Ship Dumping as a Source of New Oil Spill in Brazil's Coastline (Bahia) in Late 2023.

In the present study, we applied forensic geochemistry to investigate the origin and fate of spilled oils like tarballs stranded at the beaches of Bahia, in northeastern Brazil, in September 2023, based on their fingerprints. Saturated and aromatic compounds were assessed by gas chromatography, and the oceanic surface circulation patterns were deciphered to determine the geographic origin of the spill. Contamination by petroleum represents an enormous threat to the unique, species-rich ecosystems of the study area. The geochemical fingerprint of the oil spilled in 2023 did not correlate with those of previous events, including the one in 2019, the one in early 2022 in Ceará, and an extensive spill across the Brazilian Northeast in late 2022. However, the fingerprint did correlate with crude oils produced by Middle Eastern countries, most likely Kuwait. The oil of the 2023 spill had a carbonate marine origin from early mature source rocks. These findings, together with the moderate weathering of the 2023 tarballs and the ocean circulation patterns at the time of the event, indicate that the oil was discharged close to the shore of Brazil, to the east or southeast of Salvador, by a tanker on an international route in the South Atlantic.

Qualitative Analysis of Baltic Amber Resin by Gas Chromatography Coupled with Mass Spectrometry and the Therapeutic Potential of this Fossil Resin

ABSTRACT Objective: To analyze the molecular composition of a sample of Baltic amber taken from an amber bracelet, verify the presence or absence of compounds beneficial to human health, and discuss the therapeutic potential of this fossil resin. Material and Methods: For this, a qualitative analysis was performed by gas chromatography coupled with mass spectrometry (GC-MS system), which can perform an automated separation into individual components of amber. Results: The samples comprised terpenes and terpenoids: monoterpenoids, sesquiterpenoids, diterpenoids, hydronaphthalene, succinic acid, and isopimaric acid. These have therapeutic potential for several diseases, inhibit several stages of the inflammatory process, and improve the symptoms caused by it. Conclusion: The amber of this sample tested is formed by terpenes and terpenoids, substances with anti-inflammatory and analgesic. However, an in-depth study is needed on the release and absorption of substances in human skin or their actual effectiveness.

Weathering impacts on petroleum biomarker, aromatic, and polar compounds in the spilled oil at the northeast coast of Brazil over time.

After the wide oil spill reached the northeast of Brazil, the resurgence of oil was recorded and to evaluate this oil in detail, two samples collected in the state of Pernambuco in 2019 and 2021 were submitted to multiple analytical techniques. For both, we have found similar saturated biomarkers and triaromatic steroid ratios, implying that they are from the same spilled source. The n-alkanes, isoprenoids, and cycloalkanes were almost completely degraded due to evaporation, photooxidation, and/or biodegradation processes. The preferential loss of less alkylated PAHs than the more alkylated ones suggests that biodegradation was the most active process. This hypothesis is reinforced by the formation of mono and dicarboxylic acids assessed by GC × GC-TOFMS and ESI(-) FT-ICR MS high-resolution techniques. Furthermore, based on the ESI(-) FT-ICR MS results, three new ratios were proposed to evaluate the progress of the biodegradation process over time: Ox>2/O, SOx/SO, and SOx/N.

Patient-centered outcomes in non-small-cell lung cancer: a real-world perspective.

Aims: To assess non-small-cell lung cancer (NSCLC) patient-centered outcomes in the real world. Methods: This is a prospective study of NSCLC patients treated at a private cancer care institution in Brazil between 2014 and 2019. Results: The report comprises 337 patients. Advanced stage was associated with higher symptom burden - fatigue (p = 0.03), pain (p < 0.001) and arm pain (p = 0.022) - and worse global, social and physical functioning (all p < 0.001). In the first 2 years, most factors evolved to either improvement or stability: cough (p = 0.02), pain (p = 0.002), global functioning (p < 0.001) and emotional functioning (p < 0.001). Staging (p < 0.001), fatigue (p = 0.001) and gender (p = 0.004) were independently associated with overall survival. Conclusions: Our results demonstrate the feasibility of conducting real-world prospective analysis of patient-centered outcomes.

Lay abstract This study looked at patient-centered outcomes in lung cancer in a real-world setting. Standardized quality-of-life questionnaires were used to actively measure patients' perception of their functional well-being and health in a clinical setting. Three hundred thirty-seven patients were enrolled in a private cancer center in Brazil between 2014 and 2019. We demonstrated that patients diagnosed at advanced stages presented with more symptoms and lower capacity to perform daily activities. However, symptoms and functioning tended to improve during treatment. Our results show that it is possible to put patients at the heart of cancer care and use their experience to guide clinical approach.

Use of counter-current chromatography as a selective extractor for the diterpenequinone 7α-hydroxyroyleanone from Tetradenia riparia.

A solvent system was developed for selective isolation by high-speed counter-current chromatography (HSCCC) of the benzoquinone 7α-hydroxyroileanone, 1, a bioactive diterpene from a dichloromethane extract of Tetradenia riparia leaves. Several solvent systems were initially studied, including hexane-ethyl acetate-methanol-water in several ratios, hexane-acetone-methanol-water, hexane-ethanol-water and hexane-acetonitrile-methanol, which gave recovery rates for the target compound between 13.4 and 35.9%. The new solvent system hexane-5% aqueous Na2CO3 (1:1) was developed based on the chemical ionization reaction of the benzoquinone hydroxyl group in the basic pH of the carbonate solution, prompted by the extraction procedure used for the extraction of lapachol (a natural naphtoquinone) from a Tabebuia species wood. By using the HSCCC chromatograph as a liquid-liquid extractor with the above mentioned solvent system the recovery rate of 1 increased to 81.8%, affording the quinone with 97% purity.

A perspectiva fenomenológico-existencial na compreensão das técnicas projetivas no psicodiagnóstico infantil / The phenomenological-existential perspective in the comprehension of the projective techniques for child psychodiagnostic / La perspectiva fenomenológico-existencial en la comprensión de las técnicas proyectivas en el psicodiagnóstico infantil

O objetivo deste artigo é discutir a possibilidade de um olhar fenomenológico-existencial aos testes projetivos, amplamente usados como instrumentos de avaliação psicológica e psicodiagnóstico. Inicialmente, o conceito de projeção é mapeado em suas diversas definições, começando pela concepção psicanalítica (que, classicamente, é entendida como “a oficial” e dá suporte às leituras e interpretações dos resultados obtidos com base no traçado e nas histórias contadas pelo testando). Em seguida, serão mostradas outras perspectivas do termo, com base na visão de autores do âmbito da fenomenologia existencial, como Sartre e Merleau-Ponty. Ao longo do texto, serão feitas algumas propostas de entendimento das provas gráficas com uma metodologia fenomenológico-existencial (como exemplo, a maiêutica socrática), que não trabalha com base em critérios prévios de análise, mas entende a fundamental participação do sujeito na "doação de significados" e na devolutiva dos resultados, momento em que a análise se completa.

The purpose of this article is to discuss the possibility of an existentialphenomenological view of projective tests, widely used as instruments for psychological assessment and psychodiagnosis. Initially, the concept of projection is mapped approaching its various definitions, starting with the psychoanalytic conception (which is usually understood as the "official one", and seconds the reading and interpretation of the results obtained based on the script and history reported by the subject). Afterwards, different perspectives of the term will be shown, grounded by the vision of authors within the existential phenomenological scope such as Sartre and Merleau- Ponty. Along the text, some proposed understanding of graphic tests will be made with an existential-phenomenological methodology (for instance, Socrates’ maieutic method), which does not work based on previous analysis criteria, but understands the subject’s fundamental role in the “donation of meanings” and in the feedback of results, when the analysis is completed

El propósito de este artículo es discutir la posibilidad de una mirada existencialfenomenológica en pruebas proyectivas, ampliamente utilizadas como instrumentos de evaluación psicológica y psicodiagnóstico. Inicialmente, el concepto de proyección es observado en sus diversas definiciones, empezando con la concepción psicoanalítica (que, clásicamente, se entiende como "oficial", y da apoyo a las lecturas e interpretaciones de los resultados obtenidos con base en los dibujos y las historias contadas por los sujetos). A continuación se muestran diferentes perspectivas del término desde la visión de los autores del ámbito de la fenomenología existencial, como Sartre y Merleau-Ponty. A lo largo del texto se realizarán algunas propuestas de entendimiento de las pruebas gráficas con una metodología fenomenológicaexistencial (como por ejemplo la mayéutica socrática) que no trabaja con criterios previos de análisis, pero entiende el papel fundamental del sujeto en la "donación de significados" y en las devoluciones de los resultados, momento en el que el análisis se completa.

Evaluation of the composition of Carica papaya L. seed oil extracted with supercritical CO2.

Among the most important tropical fruit grown in the world today and in Brazil, papaya occupies a prominent place. Native to tropical America, papaya has spread to several regions of the world, and Brazil accounts for 12.74% of the world production, followed by Mexico, Nigeria and India. The culture reached a harvested area of 441,042 ha and production of 12,420,585 t worldwide. The largest interest in this fruit relies on its main constituent compounds, like vitamins A, B and C, alkaloids (carpaine and pseudocarpaine), proteolytic enzymes (papain and quimiopapain) and benzyl isothiocyanate, more known as BITC, which has anthelmintic activity. Because of that, the present work has as objective the evaluation of the efficiency and composition of the oil extracted from Carica papaya L. seeds with supercritical carbon dioxide. The experiments were performed in a unit containing mainly a high-pressure pump and a stainless steel extractor with 42 mL of volume. The sampling was performed at each 20 min until the saturation of the process. About 6.5 g of sample were fed for each experiment done at 40, 60 and 80 °C under the pressures of 100, 150 and 200 bar. Samples of the Carica papaya L. fruit were acquired in a popular market and free for personal use intended for the study. After collection, the seeds were crushed with the help of a pestle, and dried at 60 °C for 60 min. For each operational condition, the extraction curves were constructed relating cumulative mass of oil extracted in function of the operational time. The better efficiencies were found at 40 °C and 200 bar (1.33%) followed by 80 °C and 200 bar (2.56%). Gas chromatography and NMR analysis could identify an insecticide component (BITC) that enables new applications of this residue in pharmaceutical and chemical industries.

PM2.5-bound polycyclic aromatic hydrocarbons in an area of Rio de Janeiro, Brazil impacted by emissions of light-duty vehicles fueled by ethanol-blended gasoline.

The aim of this study was to characterize the PM2.5-bound polycyclic aromatic hydrocarbon (PAH) concentrations and their diagnostic ratios in an area impacted by light-duty vehicles fueled by neat ethanol and ethanol-blended gasoline. Samples were collected using a high-volume sampler, extracted, and analyzed for all 16 EPA-priority PAHs using gas chromatography/mass spectrometry (GC/MS) following the EPA 3550B Method. The most abundant PAHs were benzo[g,h,i]perylene, benzo[b]fluoranthene, benzo[a]pyrene and indeno[1,2,3-c,d]pyrene. The total mean concentration was 3.80 ± 2.88 ng m(-3), and the contribution of carcinogenic species was 58 ± 16 % of the total PAHs. The cumulative health hazard from the PAH mixture was determined, and the carcinogenic equivalents and mutagenic equivalents were 0.80 ± 0.82 and 1.17 ± 1.04 ng m(-3), respectively. Diagnostic ratios and normalized ratios were calculated for the individual samples.

Chemical characterization of bio-oils using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry.

The liquid product obtained via the biomass flash pyrolysis is commonly called bio-oil or pyrolysis oil. Bio-oils can be used as sources for chemicals or as fuels, primarily in mixtures or emulsions with fossil fuels. A detailed chemical characterization of bio-oil is necessary to determine its potential uses. Such characterization demands a powerful analytical technique such as comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS). Limited chemical information can be obtained from conventional gas chromatography coupled mass spectrometry (GC-MS) because of the large number of compounds and coelutions. Thus, GC×GC-TOFMS was used for the individual identification of bio-oil components from two samples prepared via the flash pyrolysis of empty palm fruit bunch and pine wood chips. To the best of our knowledge, few papers have reported comprehensive two-dimensional gas chromatography (GC×GC) for bio-oil analysis. Many classes of compounds such as phenols, benzenediols, cyclopentenones, furanones, indanones and alkylpyridines were identified. Several coelutions present in the GC-MS were resolved using GC×GC-TOFMS. Many peaks were detected for the samples by GC-MS (~166 and 129), but 631 and 857 were detected by GC×GC-TOFMS, respectively. The GC×GC-TOFMS analyses indicated that the major classes of components (analytes>0.5% relative area) in the two bio-oil samples are ketones, cyclopentenones, furanones, furans, phenols, benzenediols, methoxy- and dimethoxy-phenols and sugars. In addition, esters, aldehydes and pyridines were found for sample obtained from empty palm fruit bunch, while alcohols and cyclopentanediones were found in sample prepared from pine wood chips indicating different composition profiles due to the biomass sources. The elucidation of the composition of empty fruit bunch and pine wood chips bio-oils indicates that these oils are suitable for the production of value-added chemicals. The high quantity of phenol in the bio-oil of empty palm fruit bunch is of interest because phenol isolated from the bio-oil could provide an alternative to the phenol obtained from petroleum. The anhydrosugars found mainly in the bio-oil sample of pine wood chips can be isolated and fermented to produce ethanol or lipids. GC×GC-TOFMS can be used to increase the knowledge of the chemical composition of bio-oils allowing the improved usage of this attractive renewable energy source in bio-fuels.

Desenvolvimento de um programa de qualidade nos centros de pesquisa clínica da Rede Nacional de Pesquisa Clínica em Câncer: estratégia inovadora para fortalecer a condução dos estudos clínicos / Development of a quality program in clinical research centers of the National Clinical Research in Cancer: innovative strategy to strengthen the conduct of clinical trials

A inclusão do Brasil nas pesquisas clínicas multicêntricas internacionais permitiu acesso às novas tecnologias e tratamentos inovadores. Estima-se que, nos últimos 10 anos, mais de 100 mil brasileiros participaram de estudos clínicos. Cerca de 550 instituições e centros de pesquisa no Brasil estão qualificados para fazer estudos clínicos com novos medicamentos. Assim como a inovação é essencial para muitos setores da economia, a área de pesquisa clínica é uma das portas de entrada para novas tecnologias no setor de saúde. Sob a perspectiva da baixa eficácia do tratamento de algumas doenças, a competência técnico-científicae a capacidade para inovar e desenvolver novas tecnologias serão alguns fatores críticos para o crescimento dos centros de pesquisas, desde que acompanhados da implementação de padrões de qualidade. Em âmbito internacional, os programas de qualidade nos centros de pesquisa clínica estão sendo cada vezmais recomendados. Estes programas de qualidade foram objeto central desteestudo, que teve como objetivo propor um programa de qualidade para os centros de pesquisa clínica da RNPCC, tendo o INCA como centro coordenador. Foram realizadas análise documental e revisão sistemática. A análise documental baseou-se na identificação e localização das principais diretrizes internacionais e nacionais que norteiam a pesquisa clínica. Na revisão sistemática foi realizada uma busca nas bases de dados do Medline, Lilacs, Scopus, Web of Science, CINAHL e Science Direct até junho de 2012. Além disso, foram recuperados materiais adicionais por meio da busca manual em revistas científicas e das listasde referências dos artigos relevantes para a revisão. Após a busca, 769 estudos foram identificados. Destes, nove preencheram os critérios de elegibilidade e foram incluídos na revisão. Considerando a perspectiva da implementação de programas de qualidade em áreas terapêuticas específicas, observou-se que dosnove estudos incluídos, 67 por cento não estavam relacionados a nenhuma áreaterapêutica e 33 por cento estavam relacionados às áreas de oncologia e infectologia. Os elementos que predominaram para o desenvolvimento do programa de qualidade nos centros de pesquisa clínica da RNPC foram: revisão dos dados do prontuário(56 por cento); política para violação de protocolo (56 por cento); implementação e revisão dosProcedimentos Operacionais Padrão (44 por cento); revisão do Termo de Consentimento Livre e Esclarecido (44 por cento); procedimentos para corrigir as deficiências e prevenir a sua recorrência (44 por cento); treinamento da equipe (44 por cento); avaliação da aderência ao protocolo (33 por cento); auditoria externa (33 por cento) e supervisão das submissões / aprovações regulatórias (22 por cento). Considerando esses elementos foielaborado um programa de qualidade sistêmico, num contexto que prevêretroalimentação das informações e integração entre os níveis de atuação doprograma. A criação de programas de qualidade nos centros de pesquisa clínicavem sendo uma perspectiva cada vez mais considerada para o sucesso dosestudos clínicos. Os resultados encontrados neste estudo sugerem a necessidade de uma mudança no papel dos centros de pesquisa na promoção da qualidade dos estudos clínicos, que deverá ser amplamente discutida entre os atores da pesquisa clínica.

Desenvolvimento de um programa de qualidade nos centros de pesquisaclínica da Rede Nacional de Pesquisa Clínica em Câncer: estratégiainovadora para fortalecer a condução dos estudos clínicos

inclusão do Brasil nas pesquisas clínicas multicêntricas internacionais permitiuacesso às novas tecnologias e tratamentos inovadores. Estima-se que, nos últimos 10 anos, mais de 100 mil brasileiros participaram de estudos clínicos. Cerca de 550 instituições e centros de pesquisa no Brasil estão qualificados para fazer estudos clínicos com novos medicamentos. Assim como a inovação é essencial para muitos setores da economia, a área de pesquisa clínica é uma das portas de entrada para novas tecnologias no setor de saúde. Sob a perspectiva dabaixa eficácia do tratamento de algumas doenças, a competência técnico-científica e a capacidade para inovar e desenvolver novas tecnologias serão alguns fatores críticos para o crescimento dos centros de pesquisas, desde que acompanhados da implementação de padrões de qualidade. Em âmbito internacional, osprogramas de qualidade nos centros de pesquisa clínica estão sendo cada vezmais recomendados. Estes programas de qualidade foram objeto central desteestudo, que teve como objetivo propor um programa de qualidade para os centros de pesquisa clínica da RNPCC, tendo o INCA como centro coordenador. Foram realizadas análise documental e revisão sistemática. A análise documental baseou-se na identificação e localização das principais diretrizes internacionais e nacionais que norteiam a pesquisa clínica. Na revisão sistemática foi realizada uma busca nas bases de dados do Medline, Lilacs, Scopus, Web of Science, CINAHL e Science Direct até junho de 2012. Além disso, foram recuperados materiais adicionais por meio da busca manual em revistas científicas e das listasde referências dos artigos relevantes para a revisão. Após a busca, 769 estudos foram identificados. Destes, nove preencheram os critérios de elegibilidade e foram incluídos na revisão. Considerando a perspectiva da implementação de programas de qualidade em áreas terapêuticas específicas, observou-se que dosnove estudos incluídos, 67% não estavam...

The inclusion of Brazil in international multicenter clinical trials allowed access to new technologies and innovative treatments. It is estimated that over the past ten years, more than one thousand of Brazilians have participated in clinical trials. Around 550 institutions and clinical research sites are qualified to perform clinical trials with new drugs. As innovation is essential for may areas of the economy, clinical research is one of the gateways to new technologies in the health sector. From the perspective of the low efficacy of the treatment of some diseases, technical and scientific competence and ability to innovate and develop new technologies will be critical factors for the growth of clinical research sites, provided that they are accompanied by the implementation of quality standards. Internationally, quality programs in clinical research are being increasingly recommended. These quality programs were the subject of this study, which aimed to propose a quality program for clinical research sites of National Cancer Clinical Research Network, with INCA as coordinator. To that end, a systematic review and a documental analysis were performed. The documental analysis was based on the identification and location of the main national and international guidelines regarding clinical research. In the systematic review a search was carried out in thedatabases: Medline, Lilacs, Scopus, Web of Science, CINAHL and Science Directthrough June 2012. Furthermore, additional materials were recovered by manual search in specific journals and reference lists of relevant articles for the review. After the search, 769 studies were identified. Of these, nine met the eligibility criteria and were included in the review. Considering the perspective of implementing quality programs in specific therapeutic areas, it was observed that of the nine studies included, 67% were unrelated to any therapeutic area and 33% were related to oncology and infectious diseases...

Iatrogenias mais frequentes em dentística: por que não evitá-las? / Most frequent iatrogenies in dentistry: why not avoiding them?

Iatrogenias consistem em erros causados pelo profissional ao paciente, na tentativa de sanar um problema, podendo ocasionar, na maioria das vezes, o desencadeamento de processos patogênicos. Assim sendo, o presente trabalho apresenta como propósito abordar, a partir de uma revisão bibliográfica, os fatores iatrogênicos mais comuns em Dentística, decorrentes de procedimentos clínicos restauradores; os danos causados pelos mesmos na cavidade bucal; bem como a maneira mais apropriada de evitá-los. Um dos aspectos que deve ser considerado refere-se à quantidade, cada vez mais crescente, de ações judiciais movidas contra cirurgiões-dentistas, sendo necessário maior zelo e presteza desses profissionais, quando da execução de seus trabalhos. Portanto, torna-se prudente salientar que o profissional tenha domínio sobre as técnicas de restaurações e sobre os materiais odontológicos utilizados, conhecendo suas propriedades e limitações, para que as mesmas possam ser superadas e, ainda, sigam rigorosamente as instruções de seus fabricantes, permitindo que as propriedades máximas oferecidas por tais produtos sejam então alcançadas.

Objetivo The term iatrogenic concerns any disorder caused to the patient by inappropriate practice, which intends to solve some kind of problem and, as a consequence may lead to some pathogens. This paper presents, through a literature review, the most common iatrogenic factors in Dentistry, due to clinical restorative procedures. It also presents the damages caused by those factors in the oral cavity, as well as the most appropriate ways of avoid them. One of the aspects to be considered is the increasing number of prosecutions against dental surgeons, which makes necessary to be very careful when doing that kind of job. The knowledge of restorative techniques and materials together with the appropriate clinical practice provide satisfactory results, thus avoiding injury in patients.

Chemical characterization of aromatic compounds in extra heavy gas oil by comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry.

Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOFMS) was used for the characterization of aromatic compounds present in extra heavy gas oil (EHGO) from Brazil. Individual identification of EHGO compounds was successfully achieved in addition to group-type separation on the chromatographic plane. Many aromatic hydrocarbons, especially polycyclic aromatic hydrocarbons and sulfur compounds, were detected and identified, such as chrysenes, phenanthrenes, perylenes, benzonaphthothiophenes and alkylbenzonaphthothiophenes. In addition, triaromatic steroids, methyl-triaromatic steroids, tetrahydrochrysenes and tetraromatic pentacyclic compounds were present in the EHGO aromatic fractions. Considering the roof-tile effect observed for many of these compound classes and the high number of individual compounds identified, GC×GC-TOFMS is an excellent technique to characterize the molecular composition of the aromatic fraction from EHGO samples. Moreover, data processing allowed the quantification of aromatic compounds, in class and individually, using external standards. EHGO data were obtained in µgg(-1), e.g., benzo[a]pyrene were in the range 351 to 1164µgg(-1). Thus, GC×GC-TOFMS was successfully applied in EHGO quantitative analysis.

Drug testing data from the 2007 Pan American Games: delta13C values of urinary androsterone, etiocholanolone and androstanediols determined by GC/C/IRMS.

The main purpose of this article is to show the application of the CG/C/IRMS in real time during competition in the steroid confirmation analysis. For this reason, this paper summarizes the results obtained from the doping control analysis during the period of the 2007 Pan American Games held in Rio de Janeiro, Brazil. Approximately 5600 athletes from 42 different countries competed in the games. Testing was performed in accordance to World Anti-Doping Agency (WADA) technical note for prohibited substances. This paper reports data where abnormal urinary steroid profiles, have been found with the screening procedures. One 8 mL urine sample was used for the analysis of five steroid metabolites with two separate analyses by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Urine samples were submitted to GC/C/IRMS for confirmation analysis to determine the (13)C/(12)C ratio of selected steroids. Fifty-seven urine samples were analyzed by GC/C/IRMS and the delta(13)C values ( per thousand) of androsterone, etiocholanolone, 5beta-androstane-3alpha, 17beta-diol (5beta-diol), 5alpha-androstane-3alpha, 17beta-diol (5alpha-diol) and 5beta-pregnane-3alpha, 20alpha-diol (5beta-pdiol), the endogenous reference compound are presented. One urine sample with a testosterone/epitestosterone (T/E) ratio of 4.7 was confirmed to be positive of doping by GC/C/IRMS analysis. The delta values of 5beta-diol and 5alpha-diol were 3.8 and 10.8, respectively, compared to the endogenous reference compound 5beta-pdiol, which exceeded the WADA limit of 3 per thousand. The results obtained by CG/C/IRMS confirmation analyses, in suspicious samples, were conclusive in deciding whether or not a doping steroid violation had occurred.

Estrogenic activity removal of 17beta-estradiol by ozonation and identification of by-products.

This work investigated the degradation of a natural estrogen (17beta-estradiol) and the removal of estrogenic activity by the ozonation process in three different pHs (3, 7 and 11). A recombinant yeast assay (YES assay) was employed to determine estrogenic activity of the ozonized samples and of the by-products formed during the ozonation. Ozonation was very efficient for the removal of 17beta-estradiol in aqueous solutions. High removals (>99%) were achieved with low ozone dosages in the three different pHs. Several by-products were formed during the ozonation of 17beta-estradiol. However, only a few compounds could be identified and confirmed. Different by-products are formed at different pHs, which is probably due to different chemical pathways and different oxidants (O(3) and OH radical). The by-products formed at pH 11 were 10epsilon-17beta-dihydroxy-1, 4-estradieno-3-one (DEO) and 2-hydroxyestradiol, which were not formed in pH 3. Only testosterone could be observed in pH 3, whereas at pH 7 all three by-products were found. At pH 7 and 11 the applied ozone dosages were not enough to remove all the estrogenicity from samples, even though the 17beta-estradiol residual concentration for these two pHs was lower than at pH 3. Higher estrogenicity was detected at pH 11. An explanation to this fact may be that oxidation via OH radical forms more by-products with estrogenic activity. Probably, the formation of 2-hydroxyestradiol at pHs 7 and 11 is contributing to the residual estrogenicity of samples ozonized at these pHs. In this work, complete removal of estrogenic activity was only obtained at pH 3.

Influence of hydrological pulse on bacterial growth and DOC uptake in a clear-water Amazonian lake.

This study was conducted to evaluate: (1) the bacterial growth and the dissolved organic carbon (DOC) uptake in an Amazonian lake (Lake Batata) at high-water and low-water periods of the flood pulse; (2) the influence of nitrogen and phosphorus (NP) additions on bacterial growth and DOC uptake in Lake Batata at two flood pulse periods; and (3) the bioavailability of the main DOC sources in Lake Batata. Lake Batata is a typical clear-water Amazonian lake, located in the watershed of Trombetas River, Central Amazon, Brazil. Bacterial batch cultures were set up with 90% 0.2-microm filtered water and 10% inoculum from Lake Batata. N-NH(4)NO(3) and P-KH(2)PO(4), with final concentrations of 50 and 5 microM, respectively, were added to the cultures, except for controls. Extra sources of DOC (e.g., algal lysate, plant leachates) were added to constitute six distinct treatments. Bacterial response was measured by maximum bacterial abundance and rates of bacterial production, respiration, DOC uptake, and bacterial growth efficiency (BGE). Bacterial growth and DOC uptake were higher in NP treatments than in controls, indicating a consistent nutrient limitation in Lake Batata. The composition of DOC also seems to be an important regulating factor of bacterial growth in Lake Batata. Seasonally, bacterial growth and DOC bioavailability were higher at low-water period, when the phytoplankton is a significant extra source of DOC, than at high-water period, when the forest is the main source of DOC. DOC bioavailability was better estimated based on the diversity and the diagenetic stage of carbon compounds than on single classes of labile compounds. Changes in BGE were better related to CNP stoichiometry in the water, and the "excess" of organic substrates was oxidized in catabolism, despite the quality of these compounds for bacterial growth. Finally, we conclude that bacterial growth and DOC uptake vary throughout the flood pulse in clear-water Amazonian ecosystems as a result of changes in nutrient concentration and in DOC composition.

Development of a rapid and specific assay for detection of busulfan in human plasma by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry.

A sensitive and specific assay for detection of busulfan in human plasma was developed. The assay is based on rapid isolation of busulfan by liquid-liquid extraction with ethyl acetate, and detection by high-performance liquid chromatography with electrospray ionization and tandem mass spectrometry. 1,6-Bis(methanesulfonyloxy)hexane, a synthesized analogue of busulfan, was used as the internal standard (IS). The acquisition was performed in the multiple reaction monitoring mode; busulfan and the IS were detected with no interferences from plasma matrix. The method was linear over the range 5-2500 ng mL(-1), with r2 > 0.99 and a run time of only 3.5 min. The intra- and inter-assay precisions were in the ranges 2.1-11.9% and 3.2-10.1%, respectively, and the intra- and inter-assay accuracies were 92.2-107.6% and 94.7-104.1%, respectively. The absolute recoveries were 82.0% (20 ng mL(-1)), 90.6% (1000 ng mL(-1)) and 80.0% (2000 ng mL(-1)) for busulfan, and 89.1% for the IS (1000 ng mL(-1)). The limits of detection and quantification were 2 and 5 ng mL(-1), respectively. The validated method was successfully applied to analyze plasma samples obtained from six adults receiving doses of 1 mg kg(-1) in a conditioning regimen prior to bone marrow transplantation. A marked intra-patient variation in busulfan concentrations during the steady state was observed, which limits the application of pharmacokinetic modeling and suggests that continuous therapeutic monitoring is necessary for adequate individualized dosing. In this regard, the present assay brings important advantages relative to other methods described in the literature, i.e., it is highly specific and simple to perform, with a rapid chromatographic run time (3.5 min), and the whole procedure can be completed in 4-5 h, which would permit dose corrections after the third dose allowing earlier and better dosing adjustments towards the target level of busulfan.

Characterization of lubricity improver additive in diesel by gas chromatography-mass spectrometry.

The characterization of lubricity improver additives by GC-MS-SIM is an important tool for the development and monitoring of new formulations as well as for quality control of additives in diesel. A simple method for the quantification of a linoleic oil additive derivative in diesel has been developed. Calibration is performed by analysis of standard solutions containing 2-hydroxy-ethyl linoleate with pentadecanoyl propanoate as the internal standard. The proposed method permitted the quantification of the linoleate ester at a concentration of 300 microg/mL in the additived diesel. The recovery of additive and the repeatability of the quantitative results are evaluated.