Although parabens have been reported to be used as antimicrobial preservatives in personal care products, pharmaceuticals, and foodstuffs, little is known about the occurrence of these compounds in sports supplements. In this study, a simple, fast and sensitive liquid chromatography tandem mass spectrometry method for simultaneous determination of five commonly used parabens, methyl-, ethyl-, propyl-, butyl-, and benzylparaben in sports supplements was established. The analytical method was validated with the values of parameters being acceptable. The method proved reliable, accurate, and sensitive and was successfully applied for the quantitation of parabens in 85 sports supplements samples. Almost all sports supplements contained at least one of the parabens analyzed, and the total concentrations of five parabens ranged from below the limit of quantification to 145 μg g-1, with a median value of 0.171 μg g-1. Ethylparaben and methylparaben were the most frequent paraben analogs found in samples (detection rate > 60%). Propylparaben, butylparaben and benzylparaben are forbidden in food samples, their detection rates were 49.4, 21.2 and 4.7%, respectively. Therefore, our study suggests that Brazilian population may be exposed to estrogenic not allowed parabens and their harmful effects through the intake of sports food supplements.

In this study, a simple and fast procedure was developed and validated for the determination of bisphenol A (BPA) in paper products using synchronous fluorescence spectroscopy. The method was used for the determination of BPA in thirteen types of paper products, including thermal receipt papers, lottery tickets, bus tickets, business cards, mailing envelopes, flyers, napkins, printing paper, food contact paper, kitchen rolls, toilet paper, newspapers, and magazines. BPA was found in 98% of thermal receipt papers (n = 341) at concentrations ranging from below the limit of quantification (LOQ) to 27.7 mg g−1 with a geometric mean of 14.6 mg g−1 and a median of 17.7 mg g−1. The detection rate for other paper products was 96%, with BPA concentrations ranging from below the LOQ to 379 µg g−1 and a median of 17.3 µg g−1. The estimated daily intake for the adjusted bodyweight of BPA (calculated at median concentrations) through dermal absorption from handling papers was 14.5 and 1070 ng day−1 for the general population and occupationally-exposed individuals, respectively. The proposed analytical method is simple, fast, and cost-effective for the determination of BPA in paper samples. Moreover, an estimated daily exposure of Brazilians to BPA through dermal absorption from handling different types of papers is shown.

Resumo A homeostasia entre cálcio e fósforo salivares é importante para a manutenção da saúde bucal. O objetivo deste estudo foi avaliar se polimorfismos genéticos no receptor de estrógeno alfa (ESR1), receptor de estrógeno beta (ESR2) e no microRNA17 (microRNA17) estão associados com os níveis salivares de cálcio e fósforo. Saliva de 276 crianças com 12 anos de idade foi coletada com estímulo mastigatório e os níveis de cálcio e fósforo foram determinados por Espectrofotometria de Massa. O DNA genômico foi extraído da saliva remanescente e os polimorfismos genéticos em ESR1 (rs12154178, rs1884051, rs9340799 e rs2234693), em ESR2 (rs4986938 e rs1256049) e no miRNA17 (rs4284505) foram genotipados pela reação em cadeia da polimerase em tempo real utilizando sondas TaqMan. As diferenças estatísticas nas distribuições alélicas e genotípicas entre “baixo” e “alto” níveis de cálcio e fósforo foram determinadas usando os testes qui-quadrado e teste exato de Fisher. As análises foram ajustadas por sexo (alfa de 5%). O polimorfismo rs9340799 em ESR1 foi o genótipo menos comum associado com altos níveis de cálcio (p=0,03). O alelo menos comum em ESR1 rs1884051 foi associado com baixos níveis de fósforo (p=0,005) e houve um excesso de heterozigotos para miRNA17 rs4284505 entre os indivíduos com baixos níveis de cálcio salivar (p=0,002), ambos ajustados pelo sexo. Este estudo fornece evidências de que polimorfismos genéticos em ESR1 e miRNA17 estão envolvidos na determinação dos níveis de cálcio e fósforo salivares.

Abstract Homeostasis between salivary calcium and phosphorus is important for maintaining oral health. The aim of this study was to evaluate if polymorphisms in ESR1 (Estrogen Receptor Alpha), ESR2 (Estrogen Receptor Beta) and miRNA17 (microRNA17) are associated with calcium and phosphorus levels in saliva. Saliva from 276 12-year-old children were collected by masticatory stimulation and calcium and phosphorus levels were determined by Mass Spectrometry. Genomic DNA was extracted from remaining saliva and genetic polymorphisms in ESR1 (rs12154178, rs1884051, rs9340799 and rs2234693), in ESR2 (rs4986938 and rs1256049) and in miRNA17 (rs4284505) were genotyped using TaqMan chemistry and a real-time PCR equipment. Statistical differences in genotype and allele distributions between ‘low’ and ‘high’ calcium and phosphorus levels were determined using chi-square or Fisher´s exact tests. The analysis was also adjusted by sex (alpha of 5%). ESR1 rs9340799 had the less common genotype associated with higher calcium levels (p=0.03). The less common allele of ESR1 rs1884051 was associated with lower phosphorus levels (p=0.005) and there was an excess of heterozygotes for miRNA17 rs4284505 among individuals with lower calcium levels (p=0.002), both adjusted by sex. This study provides evidence that genetic polymorphisms in ESR1 and miRNA17 are involved in determining salivary calcium and phosphorus levels.

Several studies have shown endocrine-disrupting effects of parabens. Parabens are a group of antimicrobials used as preservatives in a wide variety of products, mainly in personal care products. However, little information is available regarding the occurrence of parabens in baby products. In this study, the concentrations of five commonly used parabens, methyl-, ethyl-, propyl-, butyl- and, benzyl-paraben in 50 Brazilian baby wet wipes were analyzed by liquid chromatography coupled to mass spectrometry. All samples contained parabens, and the total concentrations ranged from 16 to 332,470 ng g-1 (geometric mean: 5344 ng g-1). Methyl-paraben, ethyl-paraben, propyl-paraben, and butyl-paraben were found in >65% of the samples. 24 out of 50 samples exceed the permitted value of 0.4 % for methyl-paraben for their use in personal care products. Although, propyl-paraben and butyl-paraben are forbidden in cosmetic products designed for application on the nappy area of children under three years of age, the detection rate of them were 94 and 70 %, respectively. Based on the measured concentrations and use frequency of baby wipes the estimated daily intake of parabens was calculated. The median estimated daily intake values of total concentrations of parabens for babies of one year old was 391 ng kg-1 bw day-1. In conclusion, babies and children may be exposed to high levels of parabens through use of baby wipes. It is also worth to mention that two forbidden parabens were frequently detected.

Um método simples e rápido para a determinação de Ca, Cu, Fe, Mg, Mn, Se e Zn em sêmen bovino por espectrometria de massas com plasma indutivamente acoplado (q-ICP-MS) é descrito. Previamente as análises, 200 µL de amostras foram diluídas 1:50 em solução contendo Triton® X-100 (0,01% v/v) e ácido nítrico (0,5% v/v). Os limites de detecção foram de 0,3, 0,03, 0,2, 0,04, 0,04, 0,03 e 0,03 µg L-1 para 44Ca, 63Cu, 57Fe, 24Mg, 64Zn, 82Se e 55Mn, respectivamente. Para efeitos de comparação e validação do método, quatro amostras de sêmen bovino foram analisadas por ICP-MS pelo método proposto e por espectrometria de absorção atômica com chama (FAAS) ou espectrometria de absorção atômica em forno de grafite (GF AAS), e não foram encontradas diferenças estatísticas entre as técnicas com aplicação do teste-t (95% de confiança). Então, o método proposto foi aplicado na determinação de Ca, Cu, Fe, Mg, Mn, Se e Zn em amostras de sêmen bovino coletadas de diferentes raças, as quais são usadas em programas de reprodução animal e inseminação artificial.

A simple and fast method for the determination of Ca, Cu, Fe, Mg, Mn, Se and Zn in bovine semen by quadrupole inductively coupled plasma spectrometry (q-ICP-MS) is described. Prior to analysis, samples (200 µL) were diluted 1:50 in a solution containing 0.01% v/v Triton® X-100 and 0.5% v/v nitric acid and directly analyzed by ICP-MS. The limits of detection of the method are 0.3, 0.03, 0.2, 0.04, 0.04, 0.03 and 0.03 µg L-1 for 44Ca, 63Cu, 57Fe, 24Mg, 64Zn, 82Se and 55Mn, respectively. For purposes of comparison and method validation, four ordinary bovine semen samples were directly analyzed by ICP-MS and by flame atomic absorption spectrometry (FAAS) or graphite furnace atomic absorption spectrometry (GF AAS), with no statistical difference between the techniques at the 95% level when applying the t-test. Then, the proposed method was applied in the determinations of Ca, Cu, Fe, Mg, Mn, Se and Zn in collected samples of bovine semen from different breeds, which are used in reproduction programs and artificial insemination.

O biomonitoramento de elementos químicos é de extrema importância na avaliação da saúde humana. Entretanto, as concentrações dos elementos químicos nos fluidos biológicos são afetadas por parâmetros ambientais e fisiológicos e, consequentemente, consideráveis variações podem ocorrer entre subgrupos de populações específicas. O Brasil é um país com ampla diversidade ambiental e existe limitado conhecimento de valores de referência para elementos químicos em fluidos biológicos. A espectrometria de absorção atômica (AAS) e a espectrometria de emissão ótica com plasma acoplado indutivamente (ICP-OES) ainda são as técnicas analíticas mais comumente empregadas no biomonitoramento de elementos químicos em amostras clínicas. Entretanto, o uso da espectrometria de massas com plasma acoplado indutivamente (ICP-MS) está se tornando a cada dia mais comum nos laboratórios clínicos. Neste estudo, foi avaliado um método rápido envolvendo simples diluição da amostra para determinação de Al, Ba, Be, Cd, Co, Cu, Cs, Mn, Ni, Pb, Pt, Sb, Se, Sn, Tl e U em urina por ICP-MS. Amostras de urina (500 μL) foram pipetadas em frascos cônicos de 15 mL e diluídas para 10 mL com uma solução contendo 0,5 % (v/v) HNO3 + 0,005% (v/v) Triton X-100. Ródio, irídio e ítrio foram adicionados como padrões internos. Em seguida, as amostras foram diretamente analisadas por ICP-MS com calibração por ajuste de matriz. Os limites de detecção do método (3s, n = 20) foram da ordem de ng L-1 para todos os analitos em estudo. O método foi aplicado para a análise de 412 amostras de urina de brasileiros saudáveis e não expostos ambientalmente ou ocupacionalmente a metais para o estabelecimento de valores de referência na população brasileira. A validação dos resultados foi acompanhada pela análise de material de referência certificada de urina (SRM) 2670a proveniente do National Institute of Standards and Technology (NIST) e de materiais de referência provenientes do Institut National de Sante' Publique Du Quebec, no Canadá.

Biomonitoring of trace elements is of critical importance in human health assessment. However, trace element concentrations in biological fluids are affected by environmental and physiological parameters, and therefore considerable variations can occur between specific population subgroups. Brazil is a large country with large environmental diversity and with a limited knowledge of the reference values (baseline data) for trace elements in biological fluids. Atomic absorption spectrometry (AAS) and inductively coupled plasma emission spectrometry (ICP-OES) are still the dominant analytical techniques used for biomonitoring trace element analysis in clinical specimens. However, the use of ICP-MS is becoming more usual in clinical laboratory analysis. Then, we evaluated here a simple dilute-and-shoot method for sequential determination of Al, Ba, Be, Cd, Co, Cu, Cs, Mn, Ni, Pb, Pt, Sb, Se, Sn, Tl and U in urine by quadrupole inductively coupled plasma mass spectrometry (q-ICP-MS). Urine samples (500 µL) were accurately pipetted into conical tubes (15 mL) and diluted to 10 mL with a solution containing 0.5 % (v/v) HNO3 + 0.005% (v/v) Triton X-100. Diluted urine samples also contain rhodium, iridium and yttrium added as internal standards. After that, samples were directly analyzed by ICP-MS against matrix-matching calibration. Method detection limit (3s, n = 20) were in the ng L-1 range for all analytes. The method was applied to the analysis of 412 ordinary urine samples from Brazilian healthy and non-exposed subjects to establish reference values. Data validation was provided by the analysis of the standard reference material (SRM) 2670a toxic elements in urine (freeze-dried) (high and low levels) from the National Institute of Standards and Technology (NIST) and reference urine samples from the trace elements intercomparison program operated by the Institut National de Sante' Publique du Quebec, Canada.

A concentração de chumbo (Pb) no sangue total (Pb-B) vem sendo comumente utilizada para monitorar a exposição a este elemento químico. Entretanto, a dificuldade em avaliar a natureza exata da exposição ao Pb é dependente não só de problemas inerentes a metodologias analíticas inapropriadas, bem como da toxicocinética complexa do Pb em compartimentos de nosso corpo. Se quisermos diferenciar mais efetivamente entre o Pb que está estocado no corpo por anos daquele proveniente de uma exposição recente, deverão ser obtidas informações pela análise de outros biomarcadores de exposição. Entretanto, nenhum dos biomarcadores de dose interna para Pb é aceito pela comunidade científica como substituto ao Pb-B. O foco desta revisão está nas limitações de biomarcadores de exposição ao Pb e nas necessidades para melhorar a exatidão nas determinações. Procuramos apresentar somente os protocolos analíticos em uso corrente e tentamos avaliar a infuência de variáveis de confusão nos níveis de Pb-B. Finalmente, fizemos uma discussão sobre a interpretação dos dados de Pb-B com respeito a fontes de exposição, sejam elas endógenas e exógenas, recente ou passada, bem como a importância das determinações de Pb no cabelo, unhas, saliva, ossos, sangue (plasma e sangue total), urina, fezes e dente decíduo.

Lead concentration in whole blood (Blood-Pb) is the primary biomarker used to monitor exposure to this metallic element. However, the difficulty in assessing the exact nature of Pb exposure is dependent not so much on problems with current analytical methodologies, but rather on the complex toxicokinetics of Pb within various body compartments. If we are to differentiate more effectively between Pb that is stored in the body for years and Pb from recent exposure, information on other biomarkers of exposure may be needed. None of the current biomarkers of internal Pb dose has yet been accepted by the scientific community as a reliable substitute for a Blood-Pb measurement. This review focuses on the limitations of biomarkers of Pb exposure, and the need to improve the accuracy of their measurement. We present here only the traditional analytical protocols in current use and we attempt to assess the influence of confounding variables on Blood-Pb levels. Finally, we discuss the interpretation of Blood-Pb data with respect to both external and endogenous Pb exposure, past or recent exposure, as well as the significance of lead determinations in human specimens including hair, nails, saliva, bone, blood, urine, feces, and exfoliated teeth.

A concentração de chumbo (Pb) no sangue total (Pb-B) vem sendo comumente utilizada para monitorar a exposição a este elemento químico. Entretanto, a dificuldade em avaliar a natureza exata da exposição ao Pb é dependente não só de problemas inerentes a metodologias analíticas inapropriadas, bem como da toxicocinética complexa do Pb em compartimentos de nosso corpo. Se quisermos diferenciar mais efetivamente entre o Pb que está estocado no corpo por anos daquele proveniente de uma exposição recente, deverão ser obtidas informações pela análise de outros biomarcadores de exposição. Entretanto, nenhum dos biomarcadores de dose interna para Pb é aceito pela comunidade científica como substituto ao Pb-B. O foco desta revisão está nas limitações de biomarcadores de exposição ao Pb e nas necessidades para melhorar a exatidão nas determinações. Procuramos apresentar somente os protocolos analíticos em uso corrente e tentamos avaliar a infuência de variáveis de confusão nos níveis de Pb-B. Finalmente, fizemos uma discussão sobre a interpretação dos dados de Pb-B com respeito a fontes de exposição, sejam elas endógenas e exógenas, recente ou passada, bem como a importância das determinações de Pb no cabelo, unhas, saliva, ossos, sangue (plasma e sangue total), urina, fezes e dente decíduo.

Lead concentration in whole blood (Blood-Pb) is the primary biomarker used to monitor exposure to this metallic element. However, the difficulty in assessing the exact nature of Pb exposure is dependent not so much on problems with current analytical methodologies, but rather on the complex toxicokinetics of Pb within various body compartments. If we are to differentiate more effectively between Pb that is stored in the body for years and Pb from recent exposure, information on other biomarkers of exposure may be needed. None of the current biomarkers of internal Pb dose has yet been accepted by the scientific community as a reliable substitute for a Blood-Pb measurement. This review focuses on the limitations of biomarkers of Pb exposure, and the need to improve the accuracy of their measurement. We present here only the traditional analytical protocols in current use and we attempt to assess the influence of confounding variables on Blood-Pb levels. Finally, we discuss the interpretation of Blood-Pb data with respect to both external and endogenous Pb exposure, past or recent exposure, as well as the significance of lead determinations in human specimens including hair, nails, saliva, bone, blood, urine, feces, and exfoliated teeth.