RESUMO
Perfluorinated alkyl acids (PFAAs) have been used for 50+ years in materials such as stain-resistant treatments for paper and clothing, lubricants, and foam fire extinguishers. PFAAs are characterized by a fully fluorinated alkyl chain with a terminal acid group. Their long half-lives and ubiquitous environmental distribution create considerable concern for wildlife and human exposure. There is interest in examining temporal trends of PFAAs using the National Marine Mammal Tissue Bank (NMMTB), but NMMTB tissues are frozen and cryohomogenized in polytetrafluoroethylene (PTFE)-based materials. Because PTFE supplies may leach PFAAs into samples, this study mimicked collection, processing and storage steps of NMMTB samples and measured PFAA leaching to determine the feasibility of using this sample archive for PFAA temporal trends. We also explored concentrations in Atlantic white-sided dolphin (Lagenorhynchus acutus, WSDs) and rough-toothed dolphin (Steno bredanensis, RTDs) blubber (n=3 and 0) and liver (n=48 and 12, respectively). The materials used in NMMTB protocols may add up to 0.968ng/g perfluorooctanoic acid (PFOA), 0.090ng/g perfluorononanoic acid (PNFA), and 0.221ng/g perfluorooctane sulfonate (PFOS) to each archived sample. Leaching of PFNA and PFOS from supplies compared to dolphin levels was negligible, but PFOA contributions were substantially higher than levels found in most dolphin liver samples. Therefore, monitoring PFOA temporal trends from the NMMTB would require careful consideration. RTDs had significantly higher levels of PFOS and PFNA than WSDs. Both species have similar life history, trophic status, and foraging behaviors in deep pelagic waters, so differences could be from latitudinal variation in contamination. RTDs stranded in Florida; WSDs stranded farther north mostly in Massachusetts. Juveniles had significantly higher levels of PFOS and PFNA than adults in both species, suggesting growth dilution as they approach maturity. PFOS significantly decreased after 2001 in both species as expected based on changes in production.
RESUMO
A liquid nebulization-differential mobility analysis methodology was evaluated for the measurement of the size distribution and quantitative mass concentration of nanomaterials in environmentally relevant aqueous media. The analysis time is 8 min, and the method requires little routine sample preparation and less than 8 mL of sample. The method can be used for rapid, direct analysis of nanomaterials in aqueous media with a particular application to dose verification in ecotoxicology studies, analysis of manufacturing process waste streams, and raw material analysis. Twelve reference materials having a diameter traceable to the National Institute of Standards and Technology were spiked into 6 different aqueous matrices that included drinking water, groundwater, industrial wastewater, as well as the algae and daphnia media used in ecotoxicology testing. Measurement of the diameter of a reference material was within the expected range for the reference material. Individual response factors for each reference material were determined in each medium and the accuracy and precision of the concentration measurements evaluated. In ecotoxicology test media, measurements of the concentration of nanoparticles having diameter ≥ 30 nm, had corresponding accuracies and precisions of 103% and 7%, respectively. Over 28 d 86% of the samples had concentrations within 20% of the initial concentration. The method limit of quantification depended primarily on matrix complexity and particle diameter; the limit of quantification ranged from 0.01 mg/L to 3 g/L.
