Hidetsuru Matsushita

Identification and quantification of chlorinated bisphenol A in wastewater from wastepaper recycling plants.

Chlorinated derivatives of bisphenol A were detected in the final effluents of eight paper manufacturing plants in Shizuoka, Japan, where thermal paper and/or other printed paper is used as the raw material. Their amounts were determined by gas chromatography/mass spectrometry (GC/MS) after treatment with N, O-bis(trimethylsilyl)trifluoroacetamide, and ranged from traces to 2.0 microg/l. They are likely produced by chlorination of bisphenol A, which was released into the effluents from the pulping process of wastepaper, during or after bleaching with chlorine.

A survey on polycyclic aromatic hydrocarbon concentrations in soil in Chiang-Mai, Thailand

Abstract Soil samples were collected at 30 sampling sites along roadsides in the city of Chiang-Mai, Thailand, in February 1996, and concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined. The distribution of PAH concentration in the soil samples was almost lognormal for all PAHs. Concentrations of pyrene (Py) and fluoranthene (Fluor) were the highest, followed by those of benzo[ghi]perylene and coronene (Cor). Since PAH concentrations were highest on the roadside where the traffic density was high, vehicles were the main determinants of PAH concentration in soil in Chiang-Mai. Significant correlations among PAH concentrations were found for almost all PAHs. PAH profiles in the air were different from those in the soil. For example, relative benzo[a]pyrene (BaP) concentration in the soil was significantly lower than that in the air. Relative concentrations of Fluor, Py, chrysene, and Cor in the soil were considerably higher than those in the air, due presumably to their difference in photochemical reactivities and in sources. The sampling of soil has advantages relative to that of air: 1) collection of soil is easy; 2) it needs no special equipment and electricity; 3) it takes little time; and 4) it can be collected anywhere. Therefore, PAH analysis in soil was useful as a proxy-screening tool for air pollution levels with consideration of compositional differences between soil and air samples.

Mutagenicity of the photochemical reaction products of pyrene with nitrogen dioxide

The mutagenicity of the photochemical reaction products of pyrene with nitrogen dioxide (NO2) and the mutagens in them were investigated for the interpretation of their biological significance as genetoxic hazards of polycyclic aromatic hydrocarbons (PAHs) in airborne particles. Samples extracted from the photochemical reaction products of pyrene with NO2 diluted with air using a high-pressure mercury lamp were mutagenic for Salmonella typhimurium strains TA97 and TA98 in the absence of S9 mix, with a trend to detoxification in the presence of the metabolic system. The mutagens in the crude samples extracted from their products, which were fractionated by normal-phase high-performance liquid chromatography (HPLC) on a column of Nucleosil 100-30 with n-hexane-benzene as an eluting solution, were analyzed by HPLC, mass spectrometry and Fourier transform infrared (FT-IR) spectrometry. Based on these results, it was recognized that 1-nitropyrene (1-NP), 1,3-dinitropyrene (1,3-DNP), 1,6-dinitropyrene (1,6-DNP) and 1,8-dinitropyrene (1,8-DNP) was formed by the photochemical reaction of pyrene with NO2. The yield of DNPs peaked at 2-3 h irradiation.

A passive sampler–GC/ECD method for analyzing 18 volatile organohalogen compounds in indoor and outdoor air and its application to a survey on indoor pollution in Shizuoka, Japan

A simple and reliable method was developed for analysis of 18 volatile organohalogen compounds (VOHCs) both indoors and outdoors, consisting of VOHC collection by a passive sampler, extraction with toluene by mechanical shaking, and automatic separation analysis by capillary gas-chromatography with electron capture detector (GC/ECD). The passive sampler is a porous polytetrafluoroethylene (PTFE) tube (30.30+/-0.37 mm net collection length, 5.0 mm inside diameter, 0.990 g weight) uniformly packed with activated charcoal (194.4+/-3.8 mg). The procedure was applied to a field survey on indoor and outdoor VOHC pollution in Shizuoka, Japan. Ten VOHCs, including trichloroethylene, tetrachloroethylene, chloroform, carbon tetrachloride, and p-dichlorobenzene, were detected from indoor and outdoor air samples. The ratios of maximum to minimum VOHC concentrations, both outdoors and indoors, were large. The indoor and outdoor concentrations of 1,1-dichloroethylene, dichloromethane, 1,1,1-trichloroethylene, carbon tetrachloride and trichloroethylene were found to be similar. Indoor concentrations of trihalomethanes, p-dichlorobenzene and tetrachloroethylene were higher than those of outdoors.

Highly sensitive automatic analysis of polycyclic aromatic hydrocarbons in indoor and outdoor air

A method for the quantitation of polycyclic aromatic hydrocarbons (PAHs) in indoor and outdoor air by high-performance liquid chromatography (HPLC) with a spectrofluorometric detection and programmed excitation and emission wavelength pairs is proposed. The mobile phase is a linear gradient of methanol-water. The relative standard deviations (n = 5) are in the range 0.38-1.7% at concentration levels of 0.69-11.40 ng ml(-1). The determination limits (S N = 10 ) are 0.5-15.9 pg. The proposed method was successfully applied to quantitate 12 PAHs in gas phase and particulates in indoor and outdoor air. The recoveries of PAHs from gas phase and particulates were 95.7-117.5 and 94.8-112.4%, respectively. This highly sensitive automatic HPLC analysis for PAHs both in gas phase and particulates can be applied to indoor and outdoor survey.

Carcinogens in the indoor air of Hong Kong homes: Levels, sources, and ventilation effects on 7 polynuclear aromatic hydrocarbons

Abstract The concentration of carcinogens in the airborne dust of 33 homes in Hong Kong was studied to identify the sources and measure the amounts of 7 polynuclear aromatic hydrocarbons (PAH) including benzo(a)pyrene. The 24 hr samples were collected from kitchens and living rooms of working class homes and analyzed by HPLC. The mean levels of PAH in air and dust were comparatively low, with cooking fires and incense associated with significant increases, and window ventilating fans with significant decreases in PAH concentrations. Perceived pollution sources like water heaters, cigarette smoke, and stir‐fry cooking, led to reduced airborne PAH levels because human responses to these emission sources were to increase natural and mechanical ventilation. The data indicated that compensation behaviours can over‐ride the effects of emission sources, and help explain why measures of increased ventilation from open windows and doors were generally associated with higher PAH levels. The results of this study sh...

Collaborative study using the preincubation Salmonella typhimurium mutation assay for airborne particulate matter in Japan. A trial to minimize interlaboratory variation

A collaborative study has been performed over a period of 3 years to develop a suitable method for monitoring the mutagenicity of airborne particulate matter. The study was organized with 8 laboratories and performed in the following steps: (1) selection of a suitable technique for each process involved in the mutagenicity monitoring, (2) developing a tentative protocol by combining systematically the selected techniques, (3) evaluation of the protocol by intra- and inter-laboratory studies, (4) modification of the protocol according to the evaluation, and (5) evaluation of the modified protocol by conducting an interlaboratory study. We found a suitable method for mutagenicity monitoring of particles in the atmosphere. Airborne particles were sampled with a high-volume sampler, the samples were stored at -80 degrees C, extracted by sonication using dichloromethane, solvent-exchanged, and assayed by the preincubation method using Salmonella typhimurium TA98 and TA100. The observed mutagenic activity was normalized with that of an internal standard. Round robin tests revealed that the method resulted in excellent reproducibility. The coefficient of variation for mutagenic activities of airborne particulate samples collected in various districts of Japan were in the range of 14.7 +/- 6.6% to 19.6 +/- 4.0% for strains TA98 and TA100 with and without metabolic activation. We also found that the plate incorporation method was equivalent to the preincubation method for airborne particulate extracts.

CANCER AMONG BENZOYL CHLORIDE MANUFACTURING WORKERS

In 1974, the Workmens Accident Compensation Section of the Tokyo Labour Standards Bureau asked one of the authors whether or not the lung cancer of a worker who had worked in a chemical plant was occupational, because there had been two previous deaths due to lung cancer in this plant. This factory had produced benzoyl chloride from 1954 to 1972, and morpholine disulfite and forced plastics after 1972. The size of the plant was small. with about 20 workers usually employed. The case histories of the above three lung cancer patients are as follows: Case I. K. S . was born in 1929, and had engaged in the manufacturing of benzoyl chloride from 1955 to 1969. Since about 1965, he had suffered from frequent colds, bronchial pain, and anosmia. Around 1969, he noticed that the skin of his hands was colored black, with white and red spots and warts. Starting in 1971, he had been troubled with daily coughing. In 1972 his disease was diagnosed as pulmonary tuberculosis. In 1973, tumor shadow was found in the left hilum of the lung by x-ray examination, and was diagnosed as squamous cell carcinoma by histological examination. He was a nonsmoker. Case 2. I. A. was born in 1926, and had engaged in the manufacturing of benzoyl chloride from 1954 to 1969. He left this plant in 1969. In 1970, he suffered pain in the right chest and coughing. His disease was diagnosed as lung cancer by x-ray examination, and he underwent surgery for its excision. He died in 1972. Results of the histological examination are not known. He was a smoker. Case 3. K. H. was born in 1916 and had worked in the benzoyl chloride production plant from 1954 to 1960. Before entering this plant he had worked in another chemical plant. In 1960, tumor shadow was found in the upper lobe of the lung and he received x-ray therapy, since it was already nonoperable. He died in 1963. Nothing is known about his histological examination. He was a smoker. In addition, there was one case of cancer of another site. Case 4 . K. T. was born in 1923, and had engaged in the manufacture of benzoyl chloride from 1960 to 1970. In 1970 he noticed hemorrhagic rhinorrhea, and in 1972 his disease was diagnosed as maxillary malignant lymphoma. He died in 1973. Thus, four cases of cancer occurred among the workers who had engaged in the manufacture of benzoyl chloride. For the epidemiological study, information was collected on all persons who had worked in this plant. Lung cancer deaths there, from 1953 to 1973, were compared with the expected number of lung cancer deaths calculated from the Japanese male population during that time. Female workers were treated as male workers, statistically. They were office workers, and none of them had engaged in the manufacture of benzoyl chloride. Results are shown in TABLE 1.

Aqueous chlorination of tetracyclic aromatic hydrocarbons: reactivity and product distribution

Abstract Reaction of tetracyclic aromatic hydrocarbons (TCAHs) with chlorine in water were investigated by means of a capillary GC equipped with flame ionization detector. TCAHs tested were benz(a)anthracene (B(a)A), benzo(c)phenanthrene (B(c)P), chrysene (Chy), pyrene (Py), and triphenylene (Tri). The reactivity of these TCAHs to chlorine in water were found to be dependent on their structures, indicating a increase in the reactivity with a decrease of their ionization potentials. Mono- and dichlorinated derivatives and oxygenated compounds were identified to be present in chlorine-treated TCAHs solutions under those conditions utilized for water treatment plant.

LUNG CANCER AMONG COKE OVEN WORKERS

In the largest iron and steel works in Japan, six cases of lung cancer had been found among coke oven workers from 1947 to 1971. Labour Standard Bureau of the Ministry of Labour organized a task group of specialists to conduct an investiga-tion whether these cases should be considered as occupational. This paper is an English version of the report submitted to Labour Standard Bureau from the task group.An epidemiological survey conducted by the Ministry of Labour indicated that lung cancer incidence among retired blast furnace coke oven workers in the iron and steel works exceeded that of the expected number calculated from the general Japanese male polulation and the relative frequency of lung cancer cases to malign-ant neoplasia of all sites also exceeded that of the expected number. The task group was not able to conduct research on coke manufacturing chemical companies and manufacturing (specialized) companies because the number of lung cancer cases was too small.