Flame retardants are substances mixed with numerous materials to inhibit the combustion process, reducing risks and damages caused by fires. Among these substances, polybrominated diphenyl ethers (PBDEs) have been widely used for decades due to their low cost and high efficiency. However, since they are mixed and not chemically bonded to the materials, PBDEs can be released over time being transported through numerous pathways until they reach soils and aquatic systems, where they can accumulate in sediments and biota. Due to their high chemical stability, an essential feature for flame retardants, they are considered persistent contaminants. Several studies report the presence of PBDEs in atmospheric and aquatic particulate matter, sediments, soils and biological matrices such as marine animals, tissues and human fluids. In Brazil, little is known about the use and commercialization of PBDEs, as well as their levels in different environmental compartments. Thus, this review provides an overview of the origin of PBDEs in the environment as well as information inherent to the understanding of the behavior and presence of this contaminants of recent interest in different environmental compartments. Finally, the manuscript also brings state-of-the-art analytical approaches used for environmental sampling, preservation, preparation and sample analysis.

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Reports on the determination of emerging contaminants (EC) in aqueous samples have been increasingly common. Due to the low levels of concentration of the analytes as well as the complexity of this matrix, the analysis is done preferably by liquid chromatography (LC). Owing to the polar character of most of the EC determination by gas chromatography is deprecated. One way to overcome this barrier is through derivatization, which, in some cases, can be a lengthy step, presents risks to the analyst as well as to the environment due to the toxicity of the derivatizing agent, and, thus, ends up favoring the use of LC. An analytical protocol was developed in this work to increase the efficiency of derivatization in a shorter reaction time for the determination of ibuprofen, 4-octylphenol, 4-nonylphenol, triclosan, bisphenol A, diclofenac, estrone, 17-β-estradiol, estriol, coprostanol, and cholesterol. The proposal then was to carry out the silylation reaction of the analytes with the aid of a domestic microwave oven. The results indicated that the use of the device provided an increase in the efficiency of the reaction, due to the homogeneous heating of the solution. Besides, there was a significant decrease in the derivatization time of the analytes from 30 min to 5 min. Additionally, through a design of experiments (DOE), it was possible to perceive the influence of some instrumental parameters of GC-MS, such as temperature, pressure intensity, and pressure pulse time in the injector on the detectability of the investigated analytes. This study allowed a satisfactory separation of the analytes and an average increase in their areas of up to 35%. These aspects made it possible to obtain an analytical method with limits for the detection and quantification of EC between 0.03-11.00 ng mL-1 and 0.10-33.35 ng mL-1, respectively, and uncertainties below 9%. The developed method was applied in the determination of the analytes in coastal seawater and the determined concentrations varied from 0.24 ng L-1 for estriol and 43.60 ng L-1 for cholesterol. Thus, the improvement of the silylation reaction, combined with the strategy of instrumental optimization, proved to be simple, efficient, and fast, as well as being a comparable alternative to liquid chromatography.

A new sorbent material based on modified clay with ionic liquid immobilized into an agarose film was developed as part of this study. It was applied to determine organochlorine pollutants, like disinfection byproducts, through headspace solid-phase microextraction-gas chromatography-electron capture detection (HS-SPME-GC-ECD). The disinfection byproducts determined in this study were used as model molecules because they were volatile compounds, with proven severe effects on human health. Their presence in aquatic environments is in trace concentrations (from pg L−1 to mg L−1). They are classified as emergent pollutants and their determination is a challenge for analytical chemists. The parameters which affected the extraction efficiency, i.e., number and distance between SPME discs, salt concentration, the temperature of extraction, extraction time, and desorption time, were optimized. A wide linear dynamic range of 10–1000 ng mL−1 and coefficients of determination better than 0.997 were achieved. The limits of detection and the limits of quantitation were found in the ranges of (1.7–3.7) ng mL−1 and (5.6–9.9) ng mL−1, respectively. The precision, expressed as relative standard deviation (RSD), was better than 8%. The developed sorbent exhibits good adsorption affinity. The applicability of the proposed methodology for the analysis of trihalomethanes in environmental and water samples showed recoveries in the range of 86–95%. Finally, the newly created method fully complied with the principles of green chemistry. Due to the fact that the sorbent holder was made of agarose, which is a wholly biodegradable material, sorbent clay is a widespread material in nature. Moreover, the reagents intercalated into the montmorillonite are new green solvents, and during the whole procedure, low amounts of organic solvents were used.