The Russian tanker Nakhodka met a hull-broken accident in sailing in the Sea of Japan on January 2, 1997, releasing approximately 6200 kl of heavy oil into the Sea of Japan. The spilled oil was driven by the prevailing winds and water currents and polluted the coastline from the Shimane Prefecture through the Yamagata Prefecture. While much effort was made to remove the reached oil, many workers engaged in oil-removing complained of an eyeache, giddiness, a headache, etc. These symptoms were considered to be caused by volatile chemicals in the oil. Although the greater part of the oiled coastline was cleaned shortly after the oil pollution, there is concern that sands, rocks and sea water of the shore were still contaminated with chemicals included in the oil. Furthermore, some part has remained not to be treated. Extensive scientific studies were conducted to 1) evaluate the influence of volatile chemicals in the spilled oil on the health of oil-removing workers, 2) assess the impact of the spill on the ecosystem, 3) where and how long the contamination by the oil or chemicals persists in the environment. This paper reviews the activities and researches made after the Nakhodka oil spill accident.

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Organic compounds of particulates accumulated in the tunnel duct of freeways were extracted with a benzene-ethanol mixture solution (4 : 1, v/v) and fractionated into four fractions by 5% hydrous silica gel. The obtained organic substances were found to be composed of nonpolar, semipolar, polar and high polar compounds, by the use of GC-MS. The nonpolar fraction, in which linear alkanes ranging from C₁₆ to C₂₆ dominated, was shown to have many peaks on an extremely broad peak by GC-MS. These notable patterns were similar to those of vehicular exhausts. These observations have been characteristic of GC patterns of vehicular exhausts. The semipolar fraction was identified to contain mainly three- to four-ring polycyclic aromatic hydrocarbons (PAHs) such as phenanthrene, dibenzothiophene, fluoranthene, pyrene and chrysene/triphenylene. Their concentrations in the total mass of particulates showed 0.6-39.5 μg/g. Moreover, alkylated PAHs such as benzo [b] naphtho [2, 1-d] thiophene and cyclopenta [cd] pyrene also detected in the sample, might be used for the markers of automobile exhaust particulates. In this fraction, 64 PAHs were tentatively identified by the use of the Wiley library search system and some of them were identified finally in comparison with authentic samples by GC-MS. The polar fraction was found to include oxygenated polycyclic aromatic compounds such as 1-naphthaldehyde, phenanthrene-9-carboxaldehyde, 9-fluorenone, xanthone, benzanthrone, anthraquinone, 9, 10-phenanthrenequinone, 2-methylanthraquinone and 1, 2-benzanthraquinone. Their concentrations ranged 0.9-51.7 μg/g in the total mass of particulates and were higher than those of oxygenated PAHs in particulates collected in a rural area, urban air and indoor air. In this fraction, 44 oxygenated compounds including oxygenated polycyclic aromatic compounds were tentatively identified by the same technique described above. The high polar fraction could not be analyzed.

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The stability of 61 polycyclic aromatic hydrocarbons (PAHs) (27 nonpolar, 20 oxygenated, and 14 deuterated PAHs) in quartz fiber filters with or without airborne particulates, and acetonitrile during storage under different conditions was investigated using gas chromatography-mass spectrometry (GC-MS). Most of the investigated PAHs except 11 volatile PAHs in quartz fiber filters, and all of PAHs in acetonitrile were stable during 1 week storage and 4 week-storage in a refrigerator at 4°C, respectively. It was found that 14 PAHs in quartz fiber filters and 9 PAHs in airborne particulates decreased less than 70% under UV light during 2 weeks. Photodegradation of PAHs spiked in quartz fiber filters under UV storage was faster than those in airborne particulates. Thirty-two and 39 PAHs in acetonitrile decreased less than 70% during 2 week-storage and 4 week-storage under sunlight by the window, respectively. Photo-changed compounds such as anthracene, benz [a] anthracene, naphthacene, 9-anthraldehyde, acenaphthenequinone and anthracene-d₁₀ were tentatively identified by GC-MS. It was clarified that nonpolar and oxygenated PAHs were gradually changed into their oxygenated derivatives such as quinones and ketones. Consequently, it is recommendable that the airborne particulate sample and standard solution for PAHs should be kept without light such as in a refrigerator.

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The purity test of the Japanese Pharmacopoeia Absorbent Gauze for fluorescent whitening agents is regulated to perform by a method of irradiating the gauze with ultraviolet rays in a dark place. This method has been reported to have a difficulty in detecting the existence of fluorescent whitening agents in several cases. We, therefore, tried to establish a method to examine the existence of fluorescent whitening agents using physical and chemical methodologies. After cutting the Japanese Pharmacopoeia Absorbent Gauze samples in small pieces, fluorescent whitening agents were extracted by 30% pyridine solution at 100°C for 30 min. We analysed the fluorescent agents using reversed phase TLC, spectrofluorophotometer and HPLC with a fluorescence detector using 8 standard fluorescent whitening agents as controls. Conditions of reversed phase TLC : plate, RP-18W (Merck) ; solvent system, A) acetonitrile-water (1 : 4), B) acetonitrile-methanol-water (3 : 3 : 10), C) methyl ethyl ketone-methanol-water (1 : 1 : 1). Conditions of HPLC with fluorescence detection : column, Wakosil 5C18 (i.d. 4.6×150 mm) ; mobile phase, 0.01M ammonium acetate-acetonitrile (7 : 3) ; flow rate, 1.0 ml/min ; injection volume, 20 μl ; detections, fluorescence detector (excitation 345 nm and emission 435 nm).

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A rapid analytical method for the determination of tributyltin and triphenyltin compounds in fish was investigated. These compounds were derivatized with sodium tetraethylborate (NaBEt₄), and analysed by gas chromatography (GC) with flame photometric detection in the S mode. Tributyltin and triphenyltin compounds in fish were extracted as tributyltin chloride (TBT) and triphenyltin chloride (TPT) with 3 M hydrochloric acid and transferred to a hexane-diether ether mixture (4 : 6, v/v). The Extract was cleaned up by Florisil column chromatography. Eluate was evaporated to just dryness at 40°C. The residue was dissolved in 4 ml of hexane. For derivatization, 2 ml of extract and 10 ml of acetate buffer were placed into 20 ml vial, and subsequentry 500 μl of 1% NaBEt₄ solution was added. The vial was closed immediately, and shaken for 2 min. Hexane layer was injected into GC. Recoveries of TBT and TPT spiked to fish at the level of 0.008 μg/g or 0.05 μg/g ranged from 90.2 to 96.6%. Detection limits of TBT and TPT in the sample were 0.001 and 0.002 μg/g.

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Effects of storage conditions on the mutagenicity of human (2 smokers and 3 nonsmokers) urine were examined. Aliquots of urine from each male volunteer were stored at -80, 3, 25 and 40°C for various time points (max. 4 or 8 weeks). All extracts were obtained by the use of the Sep-pak tC₁₈/methanol method. At the end of maximum time points, all extracts were assayed by the pre-incubation method with Salmonella typhimurium YG1024. Some statistical changes of mutagenicity were observed under the storage conditions with 25 and/or 40°C for 1 or 2 weeks by the analysis of variance techniques. However, no statistical changes were observed under -80 and 3°C at least up to 4 weeks (significance level : 0.01). It was suggested that human urine samples for the mutagenicity assay may be practically stored at 3°C at least for 4 weeks.

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Physical properties were examined about Aso volcanic ash soil which is considered to be the origin of Kuroboku soil in Kumamoto prefecture. It is revealed that the volcanic ash soil is low in Al₂O₃ ratio which means its capability of becoming "active Al", and is large in pore size and small in specific surface area. The adsorption of ammonium and phosphate ions on the Aso volcanic ash soil and accompanying elution of constituent elements were examined by passing a NH₄H₂PO₄ solution (1-3300μg/ml) through a column (10 cm diameter and 75 cm long) of the soil sample. The adsorbed amounts of NH₄⁺ and PO₄^3- were 0.042 and 0.688 mg/g, respectively. Na⁺, K⁺, Ca²⁺, Mg²⁺, and SO₄^2- were eluted from the ash soil were observed during the adsorption reaction by use of 1μg/ml of the NH₄H₂PO₄ solution.

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