We evaluated the median lethal concentrations (LC50s) of the pyrithione (PT) antifoulants copper pyrithione (CuPT) and zinc pyrithione (ZnPT) to a teleost, red sea bream (Pagrus major), and a crustacean, toy shrimp (Heptacarpusfutilirostris). The 96-h LC50 values of CuPT and ZnPT, on the basis of actual concentrations, were 9.3 and 98.2 R.g/L, respectively, for red sea bream and 2.5 and 120 microg/L, respectively, for toy shrimp. Histological observations revealed that the secondary lamellae of the gill filaments of the experimental fish were heavily damaged after exposure to the PTs, suggesting that fatal hypoxemia was one cause of death. Because CuPT and ZnPT are usually used in combination with Cu, we also estimated the joint toxicities of the PTs with Cu using the LC50 values of the PTs and those of Cu (84.4 and 113 microg/L for red sea bream and toy shrimp, respectively). The results suggested that the joint toxicity of the ZnPT and Cu mixture is more than the additive toxicities of CuPT and Cu, especially in toy shrimp. The enhancement of toxicity in the mixture was inferred to be caused by conversion of ZnPT to the more toxic CuPT in the presence of Cu.

The concentrations of booster compounds were surveyed in the port of Osaka, Japan. The concentrations of Sea-Nine 211, Diuron and Irgarol 1051 in water samples from the port of Osaka were in the ranges <0·30–0·55 ng l−1, 13–350 ng l−1, 1·3–77 ng l−1, respectively. Pyrithiones were not detected in water samples. The levels of Diuron and Irgarol 1051 in the port of Osaka were high in the mooring area for small and medium-hull vessels with poor flushing.Susceptibility of bacterial populations in estuarine water to antifouling biocides was studied. Sea-Nine 211, Diuron, Irgarol 1051 and Copper pyrithione dissolved in dimethyl sulfoxide (DMSO) were added to estuarine water and number of colony forming units (CFU) of bacteria in estuarine water was counted using R2A agar plate. The CFU was not decreased at the concentration less than 1·0 mg/l of Diuron, Irgarol 1051 and Copper pyrithione. However, CFU was decreased at 0·1 mg/l of Sea-Nine 211. Degradation of Sea-Nine 211, Diuron, Irgarol 1051 and Copper pyrithione by bacteria in estuarine water was studied using a die-away method. At an initial concentrations of 0·1 mg/l, observed half-lives of Sea-Nine 211 and Copper pyrithione were 10 and 20 days, respectively. In contrast, Diuron and Irgarol 1051 were degraded scarcely during 60 days of culture.Photodegradation of these booster biocides by sunlight and UV light were studied. Under UV, all biocides were below detection limit after one day of irradiation. Under sunlight, Copper pyrithiones were also below detection limits after one day. Drastic decrease of Sea-Nine 211 concentration was observed after one day. Diuron and Irgarol 1051 scarcely decreased during 17 days of sunlight irradiation.

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 EC(50)) 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 microg 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 Cu(2+) concentration. These results indicate that in the presence of sufficient Cu(2+), 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.

Java medaka (Oryzias javanicus), which is distributed in estuarine waters of East to Southeast Asia, is proposed here for consideration as a new marine test fish. Semi-static acute toxicity tests were conducted at 26 degrees C for 1 week, 2 weeks, and 1 month old Java-medaka exposed to 4-chlorophenol and zinc, and 2 weeks olds exposed to potassium dichromate (hexavalent chromium) and sodium hypochlorite (residue chlorine). Ninety-six hours LC50s of 4-chlorophenol, zinc, hexavalent chromium, and residue chlorine were from 3.0 to 4.1, from 12.4 to 14.7, 7.4, and 0.05 mg/L, respectively. There were no large differences in sensitivity for 4-chlorophenol and zinc among the three growth stages. Compared with other fish species, these LC50s were relatively low suggesting that Java medaka has relatively high sensitivity to chemicals. This fish is quite easy to keep in the laboratory, with low mortalities at early stages and it takes about 3 months to mature from hatching, suggesting that this fish can be used not only for short-term toxicity tests but also for early life stage toxicity tests. From these results, Java-medaka is highly recommended as a marine test fish for ecotoxicity tests.

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