Degradation of triphenylborane-pyridine antifouling agent in water by copper ions.

Triphenylborane-pyridine (TPBP) is an antifouling compound used in Asian countries, including Japan, and its residue has not been detected in aquatic environments to date. There are limited data on its fate for environmental management. The purpose of this study was to evaluate whether TPBP is degraded by metal ions in aquatic environments. TPBP with metal ions in 20 mM sodium acetate buffer at pH 8.0 was placed at 25 degrees C in the dark for 24 h. The concentrations of TPBP and its degradation products, such as diphenylboronic acid, phenylboronic acid (MPB), phenol, benzene, biphenyl, and boron were determined. The presence of copper ions (50 mg/l), but not zinc or manganese ions, resulted in complete degradation of TPBP in 24 h. The TPBP degradation was much faster than the boron production in the initial reaction (0-1 h) with copper salts, depending on the copper salts tested. TPBP was degraded by copper ions (5 mg/l) in 24 h, producing phenol, MPB, biphenyl, and borate. Cu2+ as copper(II) chloride or copper(II) acetate led to complete degradation of TPBP, and thylenediaminetetraacetic acid disodium salt addition suppressed the TPBP degradation. Cu+ as copper(I) acetate also completely degraded TPBP, and bathocuproine addition suppressed the TPBP degradation. This suggests that copper ions existing in natural environments might degrade TPBP released from antifouling paint into water, and this could be one of the important mechanisms to dissipate TPBP residues in aquatic environments.

Effects of organoboron antifoulants on oyster and sea urchin embryo development.

Prohibition of Ot (organotin) compounds was introduced in Japan in 1997 and worldwide from September 2008. This meant that the production of paints containing TBT compounds was stopped and alternatives to the available Ot antifoulants had to be developed. It has been claimed that the degradation by-products of these alternative antifoulants were less toxic than those of Ot compounds. Since the introduction of the alternative antifoulants, the accumulation of these compounds has been reported in many countries. However, the toxicity of these compounds was still largely unreported. In this research, the toxicity of the alternative Ot antifoulants TPBP (triphenylborane pyridine) and TPBOA (triphenylborane octadecylamine) and their degradation products on Crassostea gigas and Hemicentrotus pulcherrimus were tested. The results showed that toxic effects in Crassostea gigas was higher for each antifouling biocide than that in Hemicentrotus pulcherrimus. Also, while the toxicity of the Organoboron antifoulants and the Ots were the same, the former's degradation products were much less harmful.

Simultaneous determination of pyridine-triphenylborane anti-fouling agent and its degradation products in paint-waste samples using capillary zone electrophoresis with field-amplified sample injection.

We proposed a capillary zone electrophoresis (CZE) procedure using field-amplified sample injection (FASI) for the simultaneous determination of pyridine-triphenylborane (PTPB) and its degradation products: diphenylborinic acid (DPB), phenylboronic acid (MPB), and phenol. The LODs for PTPB, DPB, MPB, and phenol were, respectively, 0.85, 0.88, 44, and 28 µg L(-1). The RSDs (n = 4) for the analytes listed above were in respective ranges of 6.2 - 14, 5.9 - 10, and 0.49 - 0.62% for the peak area, peak height, and migration time. The compounds were extracted from paint-waste samples collected from shipyards using a siliga-gel column. The extract was dissolved with acetonitrile containing 1% (v/v) pyridine. The samples were then analyzed using CZE, revealing respective concentrations of 0.076 - 0.53, 0.015 - 0.36, 1.7 - 22, and 1.2 - 13 µg g(-1). The proposed FASI-CZE method is a simple and promising procedure that is expected to be useful for the determination of PTPB and its degradation products in paint wastes.