Diffusive gradient in thin film for ultra-trace methylmercury measurements in the coastal and open sea

Monomethylmercury (MMHg) is a potent neurotoxin causing neurodevelopmental delays and cardiovascular and immunological issues. Human exposure primarily occurs through seafood consumption due to MMHg bioaccumulation and biomagnification from seawater into marine organisms. Determining MMHg in seawater at ultratrace concentrations poses logistical and analytical challenges. Diffusive Gradient in Thin-film (DGT) samplers represent a promising solution, which captures time-averaged concentrations by preconcentrating in situ MMHg over a defined exposure time. DGT manufactured with 3-mercaptopropyl-functionalized silica (3MFS) in agarose and polyacrylamide gels were tested and compared for the determination of MMHg present in open ocean and coastal waters. Different elution methods using acidic thiourea were tested to reach precise, accurate and quantitative elution of MMHg from the binding gel. We found that polyacrylamide-3MFS binding gels display a higher elution efficiency (94 ± 3 %), precision and better handling compared to agarose-3MFS gels (41 ± 6 %). A unique mooring line installed in the South Western Tropical Pacific Ocean, provided monthly DGT-MMHg concentrations over a year showing potential seasonal differences in MMHg concentrations ranging between 18 and 106 fM. DGT were also deployed in shallow Peruvian coastal waters, exhibiting higher MMHg concentrations (170 ± 97, n = 26) with typical benthopelagic gradients. DGT-MMHg concentrations were in good agreement with discrete water samples analyzed by reference methods using isotope dilution. DGTs offer complementary advantages over oceanographic cruises, notably in situ preconcentration, low blanks, minimal logistical requirements and cost-effectiveness. DGTs represent a valuable tool for studying the marine MMHg cycle for evaluating the implementation of the Minamata Convention.