Marine sponges as bioindicators of pollution by synthetic microfibers in Antarctica

Different marine sponge species from Tethys Bay, Antarctica, were analyzed for contamination by polyester and polyamide microplastics (MPs). The PISA (Polymer Identification and Specific Analysis) procedure was adopted as it provides, through depolymerization and HPLC analysis, highly sensitive mass-based quantitative data. The study focused on three analytes resulting from the hydrolytic depolymerization of polyesters and polyamides: terephthalic acid (TPA), 6-aminohexanoic acid (AHA), and 1-6-hexanediamine (HMDA). TPA is a comonomer found in the polyesters poly(ethylene terephthalate) (PET) and poly(butylene adipate co terephthalate) (PBAT), and in polyamides such as poly(1,4-p-phenylene terephthalamide) (Kevlar™ and Twaron™ fibers) and poly(hexamethylene terephthalamide) (nylon 6 T). AHA is the monomer of nylon 6. HMDA is a comonomer of the aliphatic nylon 6,6 (HMDA-co-adipic acid) and of semi-aromatic polyamides such as, again, nylon 6 T (HMDA-co-TPA). Except for the biodegradable PBAT, these polymers exhibit high to extreme mechanical, thermal and chemical resistance. Indeed, they are used as technofibers in protective clothing able to withstand extreme conditions as those typical of Antarctica. Of the two amine monomers, only HMDA was found above the limit of quantification, and only in specimens of Haliclona (Rhizoniera) scotti, at a concentration equivalent to 27 μg/kg of nylon 6,6 in the fresh sponge. Comparatively higher concentrations, corresponding to 2.5-4.1 mg/kg of either PBAT or PPTA, were calculated from the concentration of TPA detected in all sponge species. Unexpectedly, TPA did not originate from PET (the most common textile fiber) as it was detected in the acid hydrolysate, whereas the PISA procedure results in effective PET depolymerization only under alkaline conditions. The obtained results showed that sponges, by capturing and concentrating MPs from large volumes of filtered marine waters, may be considered as effective indicators of the level and type of pollution by MPs and provide early warnings of increasing levels of pollution even in remote areas.