Co-occurrence of microplastics and microparticles containing Cu and Zn and other heavy metals in sea-surface microlayer in Osaka Bay, Japan

Antifouling biocides such as Cu, Zn, and organic compounds not only inhibit adhesion of sessile organisms on ship hull but also possess toxicity to non-sessile organisms in marine environment. Thus, we firstly investigated the heavy metals and polymer types of anthropogenic microparticles (MPs) floating in the sea-surface microlayer (S-SML) in Osaka Bay. 7 types of MPs containing different metals (Cu, Cu-Zn, Zn, Ti, Sn, Ba and Fe-Mn-Ni) were found. The polymer type for 97.8 % of Cu and Cu-Zn MPs (41 samples) and 52.6 % of Zn MPs (19 samples) was acrylic resins which are widely used as binders in contemporary antifouling paints for ships; concentrations of 511-54,000 mg/kg for Cu and 95.1-13,200 mg/kg for Zn were found in these MPs. The high metal concentrations found the co-existence of acrylic polymers point towards an origin from antifouling paint particles (APPs). Furthermore, to quantify Cu and Zn concentrations in these MPs based on X-ray fluorescence spectroscopy (μ-XRF), calibration curves obtained from standard paint particles containing different Cu and Zn concentrations and different particle sizes made with similar matrix used in commercial antifouling paint were firstly established, according to which highly reliable Cu and Zn concentrations in MPs were obtained.