RESUMO
Phthalates or phthalic acid esters (PAE) and bis(2-ethylhexyl)adipate (DEHA) are ubiquitous chemicals often used as plasticisers and additives in many industrial products and are classified as both persistent organic pollutants (POPs) and new emerging pollutants (NEPs). Exposure to these chemicals, especially through inhalation, is linked to a wide range of negative health effects, including endocrine disruption. Air particulate matter (PM) with an aerodynamic diameter ≤ 2.5 µm can be enriched with PAEs and DEHA and if inhaled can cause multi-system human toxicity. Therefore, proper monitoring of PAEs and DEHA in PM is required to assess human exposure to these pollutants. In this work, we developed and validated a new and sensitive gas-chromatography high-resolution mass spectrometry (GC-HRMS) method for targeted analysis of PAEs including dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), bis(2-ethylhexyl)adipate (DEHA), bis(2-ethylhexyl)phthalate (DEHP), di-n-octyl phthalate (DOP), in PM. Analytical aspects including sample preparation steps and GC-HRMS parameters, e.g., quadrupole isolation window, to enhance method sensitivity have been assessed. The estimated limit of detection (LODs) of target PAEs and DEHA ranged from 5.5 to 17 pg µL-1, allowing their trace-level detection in PM. Extraction efficiencies of 78-101% were obtained for the target compounds. Low DMP and DEP extraction efficiencies from the spiked filter substrates indicated that significant losses of higher volatility PAEs can occur during the sample collection when filter-based techniques are used. This work is the first targeted method based on GC-Orbitrap MS for PAEs and DEHA in environmental samples. The validated method was successfully applied for the targeted analysis of PAEs and DEHA in PM2.5 samples from the eighth most populous city in Brazil, Curitiba. This work is the first to report DBP, DEHA, DEHP, and DOP in urban PM from Brazil. The observed concentrations of PAEs (up to 29 ng m-3) in PM2.5 from Curitiba may not represent the extent of pollution by these toxic compounds since the analysed samples were collected during a COVID-19 restriction when anthropogenic activities were reduced.
Assuntos
Dietilexilftalato , Poluentes Ambientais , Ácidos Ftálicos , Humanos , Material Particulado/análise , Dietilexilftalato/análise , Ésteres/análise , Brasil , Ácidos Ftálicos/análise , Dibutilftalato/análise , Adipatos/análise , Poluentes Ambientais/análiseRESUMO
Per- and polyfluoroalkyl substances (PFAS), often referred to as "forever chemicals", are a class of man-made, extremely stable chemicals, which are widely used in industrial and commercial applications. Exposure to some PFAS is now known to be detrimental to human health. By virtue of PFAS long residence times, they are widely detected in the environment, including remote locations such as the Arctics, where the origin of the PFAS is poorly understood. It has been suggested that PFAS may be transported through contaminated waters, leading to accumulation in coastal areas, where they can be aerosolised via sea spray, thereby extending their geographical distribution far beyond their original source regions. The aim of this work is to investigate, for the first time, whether "forever chemicals" could be transported to areas considered to be pristine, far from coastal sites. This study was performed at the Amazonian Tall Tower Observatory (ATTO), a unique remote site situated in the middle of the Amazon rainforest, where a restricted PFAS, perfluorooctanoic acid (PFOA), was observed with concentrations reaching up to 2 pg/m3. A clear trend of increasing concentration with sampling height was observed and air masses from the south over Manaus had the highest concentrations. Atmospheric lifetime estimations, removal mechanisms supported by measurements at two heights (320 and 42 m above the rainforest), and concentration spikes indicated a long-range transport of PFOA to pristine Amazon rainforest. Potential sources, including industrial activities in urban areas, were explored, and historical fire management practices considered. This research presents the first measurements of PFAS in the atmosphere of Amazon rainforest. Remarkably, even in this remote natural environment, appreciable levels of PFAS can be detected. This study provides valuable insights into the long-range transport of the anthropogenic "forever chemical" into a remote natural ecosystem and should raise awareness of potential environmental implications.
Assuntos
Poluentes Atmosféricos , Atmosfera , Monitoramento Ambiental , Fluorocarbonos , Poluentes Atmosféricos/análise , Fluorocarbonos/análise , Atmosfera/química , Brasil , Caprilatos/análise , Floresta ÚmidaRESUMO
Introdução: Doenças alérgicas afetam de 10 a 30% da população mundial, e polens são frequentes desencadeantes. A polinose é doença decorrente da sensibilização ao pólen e é a forma sazonal da rinite alérgica e/ou asma mediada pela imunoglobulina E (IgE). A família Poaceae tem o maior número de gêneros de plantas que contribuem para a polinose, pois liberam alta quantidade de pólen na atmosfera e são largamente distribuídas. Objetivo: O presente trabalho quantificou a concentração de polens da família Poaceae na atmosfera de Curitiba e comparou a curva de distribuição de polens com os dados das décadas de 1980 e 90. Também classificou a concentração diária de pólen de gramíneas segundo a National Allergy Bureau (NAB). Método: O equipamento de amostragem foi o captador volumétrico Hirst, instalado a uma altura de aproximadamente 25 metros. Resultados: O pico de concentração diária de pólen total ocorreu no começo do mês de agosto, correspondendo a 302 grãos/m3. O mês de agosto também concentrou oito dos maiores picos diários de pólen total, sendo sete deles superiores a 200 grãos/m3. Foi encontrado pólen Poaceae ao longo de todo o ano e o maior pico de concentração foi de 27 grãos/m3 em agosto e setembro. Nas décadas de 80 e 90, os picos de polens foram no mês de novembro e período de polinização entre outubro e abril. Isso não foi observado no ano de 2018, uma vez que a época de polinização das gramíneas se adiantou, com início em agosto, e o pico de concentração foi em de agosto e setembro. Conclusão: Este estudo mostra que houve mudança na estação polínica. Os dois picos de dispersão de polens de Poaceae se repetem ao longo dos anos, mas têm sido encontrados em outros meses. Pacientes com alergia a polens podem ter sintomas por exposição fora das estações determinadas anteriormente.
Background: Allergic diseases affect 10% to 30% of the world population, with pollen as a major trigger. Pollinosis results from sensitization to pollen and is the seasonal form of allergic rhinitis and/or immunoglobulin E (IgE)-mediated allergic asthma. The Poaceae family is distributed worldwide and has the largest number of plant genera contributing to pollinosis, as they release large amounts of pollen into the atmosphere. Objective: To quantify pollen grains from the Poaceae family in the atmosphere of Curitiba, compare the pollen distribution curve with data from the 1980s and 1990s, and classify the daily concentration of grass pollen according to the National Allergy Bureau (NAB). Method: A Hirst-type volumetric sampler was placed at approximately 25 meters from the ground. Results: The peak of daily total pollen concentration occurred in early August, corresponding to 302 grains/m3. August also had 8 of the highest daily total pollen concentrations, 7 of which were greater than 200 grains/m3. Poaceae pollen was found throughout the year, with the highest concentration peak of 27 grains/m3 in August and September. In the 1980s and 1990s, the pollen peaks occurred in November and the pollen season occurred between October and April. In 2018, however, the pollen season started earlier, in August, and the pollen peaks occurred in August and September. Conclusion: This study shows a change in the grass pollen season. Although the 2 peaks of Poaceae pollen dispersion have repeated over the years, grass pollen is currently observed in other months of the year. Patients with pollen allergy may experience symptoms from allergen exposure outside the previously established grass pollen seasons.