Toxicity of Metal Pyrithione Photodegradation Products to Marine Organisms with Indirect Evidence for Their Presence in Seawater

We evaluated the acute toxicities of the metal pyrithiones (MePTs)-copper pyrithione (CuPT) and zinc pyrithione (ZnPT)-to four species of marine algae and a marine crustacean (Tigriopus japonicus). We also performed acute toxicity tests using six of the main MePT photodegradation products: pyridine-N-oxide (PO); 2-mercaptopyridine (HPS); pyridine-2-sulfonic-acid (PSA); 2-mercaptopyridine-N-oxide (HPT); 2,2'-dithio-bis-pyridine ([PS](2)); and 2,2'-dithio-bis-pyridine-N-oxide ([PT](2))-and three marine organisms representing three trophic levels: an alga (Skeletonema costatum), a crustacean (T. japonicus), and a fish (Pagrus major). The acute toxicity values (72-h EC50) of CuPT, ZnPT, HPT, (PT)(2), (PS)(2), HPS, PO, and PSA for S. costatum, which was the most sensitive of the test organisms to the chemicals tested, were 1.5, 1.6, 1.1, 3.4, 65, 730, > 100,000, and > 100,000 mu g l(-1), respectively. CuPT was detected in the growth media used for S. costatum tests and in seawater containing HPT or (PT)(2); the concentration of CuPT in seawater containing HPT was highly dependent on the Cu2+ concentration. These results indicate that in the presence of sufficient Cu2+, the toxicities of HPT and (PT)(2) should be assessed as CuPT because in Japan MePTs are most frequently used as antifouling booster biocides in conjunction with cuprous oxide.