Os ftalatos e alquilfenóis são grupos de substâncias classificadas como interferentes endócrinos (IE) por órgãos internacionais, portanto a presença destes nas diversas matrizes ambientais é preocupante, visto que mesmo em concentrações muito baixas são capazes de alterar o funcionamento normal de um organismo podendo causar anomalias no sistema reprodutor animal, câncer, obesidade, infertilidade, entre outros. No Brasil, há poucos estudos sobre a ocorrência e comportamento de ftalatos e alquilfenóis no meio ambiente. Desta forma, o objetivo desse trabalho foi estudar a presença do dimetil ftalato (DMP), dietil ftalato (DEP), dibutil ftalato (DBP), benzilbutil ftalato (BBP), bis(2-etil-hexil) ftalato (DEHP), di-n-octil ftalato (DnOP), 4-octilfenol (4-OP), 4-terc-octilfenol (4-t-OP) e 4-nonilfenol (4-NP) em água bruta e potável provenientes do rio Guandu, localizado no Estado do Rio de Janeiro, Brasil, e avaliar seus potenciais estrogênicos. Para isto, entre março e dezembro de 2015, foram realizadas 6 coletas: de água bruta, do rio Guandu, nos municípios de Nova Iguaçu e Japeri, e de água potável, em Nova Iguaçu, próximo à estação de tratamento de água da região. Uma metodologia analítica foi desenvolvida utilizando extração em fase sólida combinada à cromatografia gasosa de alta resolução acoplada à espectrometria de massas em modo seletivo de íons (EFS-CGAR-EM-MSI) para a separação e determinação simultânea dos IE estudados. O menor limite de detecção (LD) do método foi de 3,6 μg.L-1, para o DMP e o maior LD foi de 51,7 μg.L-1, para o DnOP. As curvas dos padrões sintéticos obedeceram aos critérios do INMETRO, apresentando boa linearidade, com r > 0,90. O DEHP foi o que apresentou maior concentração em todas as amostras, sendo que em 50% das amostras de água bruta e em 40% das amostras de água potável essa substância foi encontrada em níveis de concentrações superiores a 1000 ng.L-1. O 4-t-OP variou de 0,05 a 0,97 μg.L-1 e de 0,13 a 0,27 μg.L-1, nas amostras de água bruta e potável, respectivamente. Essas concentrações excedem o valor determinado pela Final European Union 2455/2001/EC, que estabelece um limite de 0,01 μg.L-1 dos isômeros de octilfenóis em águas superficiais. Foi aplicado o ensaio in vitro Yeast Estrogen Screen (YES) para a determinação da atividade estrogênica das soluções dos padrões sintéticos e das amostras, onde somente o DMP e o 4-t-OP apresentaram estrogenicidade e uma curva sigmoidal semelhante à do 17β-estradiol, enquanto que o BBP, 4-OP e 4-NP apresentaram pouca resposta estrogênica nas faixas de concentração analisadas. 75% das amostras de água bruta do rio Guandu analisadas apresentaram atividade estrogênica e o valor do EQ-E2 máximo encontrado foi de 31,9 ng.L-1, o que é preocupante, visto que concentrações superiores a 1 ng.L-1 podem causar riscos à saúde de seres humanos e animais. Com base nos resultados avaliados, pode-se concluir que o método analítico desenvolvido e sua aplicação foi uma importante contribuição para o estudo de IE em águas do rio Guandu

 According to the World Health Organization, infertility is a public health problem that affects around 48 million couples and 186 million individuals worldwide. Endocrine disruptors are one of the causes that raise more concern, given that it is a problem that has evolved with the progress of society. Many chemicals are used by food industry, entering food chain, and directly affecting human health. Endocrine disruptors have the capacity of interfering with the normal hormonal action, metabolism, and biosynthesis, which can lead to a variation of the normal hormonal homeostasis. Some of these endocrine disruptors are highly associated with diseases that are positively correlated with female infertility, such as polycystic ovary syndrome, endometriosis, irregular menstrual cycle and also disturbances on processes as steroidogenesis and development of the ovarian follicles.

Phthalates are a class of endocrine disruptors extensively used in plastic production as plasticizers, and as a result, they can be found in foods as a result of their migration ability. The occurrence of phthalates was monitored in 20 Portuguese wines using a simple, reliable, and environmentally friendly analytical method, headspace solid-phase microextraction combined with gas chromatography−mass spectrometry. Satisfactory figures of merit of method, linearity (correlation coefficient of ≥0.992), recovery (80.3−107.6%), precision (relative standard deviation of <13%), and limits of detection (0.03−0.11 μg/L) and quantification (0.09−0.36 μg/L) were achieved. Dibutyl phthalate and di-n-octyl phthalate were found in measurable quantities in table and fortified wines. The obtained results revealed that these wines do not represent any concern for human exposure, because their concentrations were lower than the tolerable daily intakes established by the European Food Safety Authority.

A investigação científica nas ciências ambientais e biológicas preocupa-se cada vez mais dos efeitos adversos das atividades humanas. A poluição por plásticos tem recebido atenção global devido ao seu evidente impacto ambiental, especialmente nos ecossistemas marinhos. Os microplásticos (MPs), definidos como partículas de plástico com menos de 5 mm, são de particular preocupação devido à sua persistência e capacidade de se infiltrar nas cadeias alimentares. No entanto, o ambiente pelágico continua a ser um dos ambientes menos explorados e mais desafiantes para estudar. Este estudo teve como objetivo investigar a presença de microplásticos numa cadeia alimentar pelágica num ecossistema oceânico, examinando em simultâneo a ocorrência de aditivos plásticos, especificamente os ftalatos (PAEs), como potenciais “tracers”. A amostragem ao longo de um ano das águas superficiais ao redor de uma ilha oceânica revelou uma presença consistente de MPs, especialmente microfibras, com flutuações sazonais significativas na razão entre MPs e zooplâncton. A análise do conteúdo estomacal das espécies de peixes pelágicos e lulas mais prevalentes que habitam estas águas confirmou que a maioria dos indivíduos ingeriu MPs, e foi observada uma correlação entre a abundância de MPs e a concentração de PAEs, particularmente DIBP (di isobutyl phthalate), nos seus tecidos. A análise de PAEs em amostras de biópsia de cetáceos que se alimentam destas presas, revelou uma presença persistente e alarmantemente elevada destes aditivos plásticos. Isso sugere uma exposição crônica e duradoura, provavelmente por meio de transferência trófica. A utilização de indicadores indiretos, como os aditivos plásticos, revela-se de grande importância em ambientes de difícil acesso e investigação, especialmente ao estudar animais protegidos, como a megafauna marinha, na qual as amostras são limitadas e de difícil obtenção. Neste estudo, foram desenvolvidas e validadas metodologias inovadoras para a deteção e quantificação de PAEs em biota marinho. A deteção de MPs e PAEs em vários níveis desta teia trófica oceanopelágica destaca a presença generalizada destes contaminantes antropogénicos mesmo em regiões oceânicas remotas.

Phthalates are multifunctional synthetic chemicals found in a wide array of consumer and industrial products, mainly used to improve the mechanical properties of plastics, giving them flexibility and softness. In the European Union, phthalates are prohibited at levels greater than 0.1% by weight in most food packaging. In the current study, headspace solid-phase microextraction (HS SPME) combined with gas chromatography-mass spectrometry (GC-MS) was optimized, through the multivariate optimization process, and validated to evaluate the occurrence of four common phthalates, di-iso-butyl phthalate (DIBP), butyl-benzyl phthalate (BBP), di-n-octyl phthalate (DOP), and 2,2,4,4-tetrabromodiphenyl (BDE), in different food packaging. The best extraction efficiency was achieved using the polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber at 80 ◦C for 30 min. The validated method showed good linearity, precision (RSD < 13%), and recoveries (90.2 to 111%). The limit of detection (LOD) and of quantification (LOQ) ranged from 0.03 to 0.08 µg/L and from 0.10 to 0.24 µg/L, respectively. On average, the phthalates concentration varied largely among the assayed food packaging. DIBP was the most predominant phthalate in terms of occurrence (71.4% of analyzed simples) and concentration (from 3.61 to 10.7 µg/L). BBP was quantified in only one sample and BDE was detected in trace amounts (<LOQ) in only two samples.

Phthalates are a group of chemicals used in a multitude of important industrial products (e.g., medical devices, children’s toys, and food packages), mainly as plasticizers to improve me chanical properties such as flexibility, transparency, durability, and longevity of polyvinyl chloride (PVC). The wide occurrence of phthalates in many consumer products, including foods (e.g., bottled water, soft drinks, wine, milk, and meat) brings that most people are exposed to phthalates every day, which raises some concerns. Adverse health outcomes from phthalates exposure have been associated with endocrine disruption, deformities in the human reproductive system, increased risk of preterm birth, carcinogen exposure, among others. Apprehension related to the health risks and ubiquitous incidence of phthalates in foods inspires the development of reliable analytical approaches that allow their detection and quantification at trace levels. The purpose of the current review is to provide information related to the presence of phthalates in the food chain, highlighting the health risks associated with their exposure. Moreover, an overview of emerging extraction procedures and high-resolution analytical approaches for a comprehensive quantification of phthalates is presented.

This paper presents an integrated approach to estimate the exposure of the Portuguese population to phthalates as a contaminant originating from paperboard packaging. The approach combined data of migrant concentration in the foods resulting from a stochastic simulation with consumption data of food packaged in paperboard. The results from the exposure model were validated with experimental values actually found in the food. A short surveillance exercise was conducted with samples collection from market shelves to identify and quantify the phthalates present in both the packages and the food. The distribution of values for the di-butyl phthalate concentration in the packages was used as the input of the initial concentration in the Weibull model to estimate the concentration of this phthalate in the foods. This distribution of occurrence data was then combined with the packaging usage data in a probabilistic simulation with a Monte Carlo sampling method. Exposure values ranged between zero and 8.95 mg day 1 kgbw, a value close to the tolerable daily intake established by the European Food Safety Authority (EFSA) – 10 mg day 1 kgbw. However, the 97.5th percentile and the average were 1.82 and 0.44 day 1 kgbw, respectively, indicating that further refinement of the estimates is not necessary. Other phthalates were also detected in the packaging samples: di-isobutyl phthalate and di-ethylhexyl phthalate. The latter was present in all packaging samples collected and was detected in a few food samples at values requiring further investigation.

Phthalates are ubiquitous contaminants in the environment and consumer products. They are used as plasticizers in many plastics used for packaging and articles for food processing, handling and storage. Some phthalates and their metabolites are known to be toxic to reproduction and endocrine disruptors, and consumer exposure has been a concern. Olive oil is of great nutritional and economic importance and its contribution to overall dietary exposure to phthalates may be relevant. This work aimed at analysing phthalates occurrence in olive oil samples collected in the European market. An alternative method for sample introduction into the chromatographic system was compared to the traditional liquid extraction followed by concentration prior analyses. The ChromatoProbe method presented similar performance regarding the limits of detection and quantification but, contrary to other matrixes like wine, does not eliminate the need for prior liquid extraction. The main advantage relies on not requiring the concentration step and on decreasing the system stoppages for maintenance. Regarding the olive oil samples collected, DEHP and DINP were detected in all samples with an average concentration of 1.31 and 1.52 mgkg(-1) and with a highest concentration of 7.52 and 6.29 mgkg(-1), respectively. Results show 4/16 samples with DEHP concentration higher than the migration limits applicable under food contact materials regulation. One of the samples is pomace oil and therefore the source of contamination may well be the solvent used in the extraction process. But the other 3 samples are extra-virgin and virgin olive oils. So it is still important to develop efforts in tracing back the source of contamination.