Kazuhiko Akutsu

Time-trend (1973–2000) of polybrominated diphenyl ethers in Japanese mother’s milk

The time-trend and recent concentrations of polybrominated diphenyl ethers (PBDEs) in Japanese mothers milk were investigated. The time-trend of 16 PBDEs (BDE-28, 37, 47, 66, 71, 75, 77, 85, 99, 100, 119, 153, 154, 138, 183, and 190) in pooled milk samples from mothers living in Osaka between 1973 and 2000 was analyzed. Additionally, PBDE concentrations in individual milk samples collected from 13 mothers living in Kanagawa and Okayama in 1999 were measured. The total concentration of all PBDE congeners (SigmaPBDEs) measured in the pooled samples increased during the period between 1973 (<0.01 ng/g lipid) and 1988 (1.64 ng/g lipid), and remained low afterwards while showing remarkable changes in PBDE congener profiles. The SigmaPBDEs in the 1999 individual milk samples were also low (0.56-3.97 ng/g lipid), except for a single sample (291 ng/g lipid). The source of this exposure could not be identified.

GC/MS analysis of polybrominated diphenyl ethers in fish collected from the Inland Sea of Seto, Japan

Development of an analytical method for polybrominated diphenyl ethers (PBDEs) in fish and their concentration in Japanese marine fish were investigated. Fish homogenate was extracted with diethyl ether/hexane (1 + 3). The extract was cleaned up by automated gel permeation chromatography (GPC) and then by mini-column chromatography, which consisted of three layers of silica gel and sulfuric acid-impregnated silica gel. The PBDE fraction was concentrated and injected into a GC/MS with negative chemical ionization (NCl). Recoveries of the 15 individual PBDEs (BDE-15, 28, 37, 47, 66, 71, 75, 77, 85, 99, 100, 119, 153, 154, and 209) each at a fortification level of 4 ng/g lipid were in the range of 88-128% and the relative standard deviations (RSD) were 0.43-7.6% (n = 4). Seven species of marine fish (conger eel, flounder, gray mullet, horse mackerel, red sea bream, sea bass, and yellowtail) were collected from the Inland Sea of Seto, and were analyzed with the developed method. Seven PBDEs (BDE-28, 47, 66, 99, 100, 153, and 154) were detected in all the samples. The most abundant PBDE congener was BDE-47 found in all the samples. Relatively high levels of PBDEs were found in the gray mullets and yellowtails.

Comparison of polycyclic aromatic hydrocarbons and nitropolycyclic aromatic hydrocarbons in airborne particulates collected in downtown and suburban Kanazawa, Japan

In this study, airborne particulates were collected at three sites, two in a downtown area and the other in a suburban area of Kanazawa, Japan in each season for 7 years. Two polycyclic aromatic hydrocarbons (PAHs), pyrene (Py) and benzo[a]pyrene (BaP) and four nitropolycyclic aromatic hydrocarbons (NPAHs), 1-nitropyrene (NP) and 1,3-, 1,6-, and 1,8-dinitropyrenes (DNP) were determined by high-performance liquid chromatography with fluorescence and chemiluminescence detection. At the downtown sites, the mean concentration of each DNP was about two orders of magnitude lower than that of 1-NP and more than three orders of magnitude lower than those of Py and BaP. This tendency reflected the composition of PAHs and NPAHs in diesel-engine exhaust particulates. Concentrations of these PAHs and NPAHs were higher at the downtown sites than at the suburban site, suggesting the dilution of these compounds during the transportation from the downtown to the suburban area. The concentration ratios of NPAHs to PAHs were larger at the downtown sites than at the suburban site. Studies using UV light and sunlight showed that degradation of NPAHs was faster than that of PAHs. Thus, the lower concentrations of NPAHs in the suburban sites may be due to their being photodegraded faster than PAHs during the atmospheric transportation from the downtown area to the suburban area.

Comparison of Polycyclic Aromatic Hydrocarbons and Nitropolycyclic Aromatic Hydrocarbons in Airborne and Automobile Exhaust Particulates

Abstract Polycyclic aromatic hydrocarbons (PAH) and nitropolycyclic aromatic hydrocarbons (NPAH) in airborne particulates collected simultaneously at downtown and suburban sites and in exhaust particulates from diesel and gasoline engine vehicles were determined. The mean concentrations of all compounds in the atmosphere were lower at the suburban site. The differences between the two sites were smaller in airborne particulates than in the atmosphere. However, the difference in NPAH concentrations in particulates between the two sites was greater than the difference in PAH concentrations, suggesting that the NPAH were less stable than the PAH. The concentrations of 1-nitropyrene and 1,3-, 1,6- and 1,8-dinitropyrenes were generally much higher in automobile exhaust particulates than in airborne particulates because the former were collected directly. However, 2-nitrofluoranthene and 2-nitropyrene were observed in airborne particulates but not in automobile exhaust particulates. The diurnal concentrations showed that 2-nitrofluoranthene and 2-nitropyrene might be formed by a hydroxyl radical-initiated reaction followed by nitration.

Detection of Dechlorane Plus and brominated flame retardants in marketed fish in Japan.

Fish samples purchased from Japanese markets were analyzed for Dechlorane Plus (DP)(syn-, anti-), polybrominated diphenyl ether (PBDE), and hexabromocyclododecane (HBCD)(α, γ). Twenty fish were analyzed using gas chromatography-mass spectrometry for DP and PBDE, and using liquid chromatography-tandem mass spectrometry for HBCD. DP was detected in 18 samples and ∑DP concentrations were <0.2-14.2 pg g(-1)wet wt. Among the DP isomers, anti-DP was the dominant residue observed in this study. PBDE was detected in all samples. Concentrations of ∑PBDE ranged from 2.2 to 878 pg g(-1) wet wt. HBCD was detected in 18 samples, and ∑HBCD concentrations were <0.02-21.9 ng g(-1)wet wt. In fish landed near the East China Sea and the Sea of Japan, we detected relatively high concentrations of DP, PBDE, and HBCD. These results indicate that the seawaters around East Asia are contaminated with flame retardants. This study demonstrates the presence of DP in fish marketed in Japan for the first time.

Dietary intake estimations of polybrominated diphenyl ethers (PBDEs) based on a total diet study in Osaka, Japan

This study presents the results of a total diet study performed for estimating the dietary intake of polybrominated diphenyl ethers (PBDEs) in Osaka, Japan. The concentrations of 36 PBDEs were measured in samples from 14 food groups (Groups I–XIV). PBDEs were detected only in Groups IV (oils and fats), V (legumes and their products), X (fish, shellfish, and their products), and XI (meat and eggs) at concentrations of 1.8, 0.03, 0.48, and 0.01 ng g−1, respectively. For an average person, the lower bound dietary intakes of penta- and deca-formulations were estimated to be 46 and 21 ng day−1, respectively. A high proportion of the decabrominated congener (DeBDE-209) was observed in Group IV. To confirm the presence of DeBDE-209 in vegetable oils, an additional analysis was performed using 18 vegetable oil samples. Of these, seven contained ng g−1 levels of DeBDE-209.

Multiresidue analysis of pesticides in vegetables and fruits using two-layered column with graphitized carbon and water absorbent polymer.

A high-throughput multiresidue analysis of pesticides in non-fatty vegetables and fruits was developed. The method consisted of a single extraction and a single clean-up procedure. Food samples were extracted with ethyl acetate and the mixture of extract and food dregs were poured directly into the clean-up column. The clean-up column consisted of two layers of water-absorbent polymer (upper) and graphitized carbon (lower), which were packed in a reservoir (75 ml ) of a cartridge column. The polymer removed water in the extract while the carbon performed clean-up. In a recovery test, 110 pesticides were spiked and average recoveries were more than 95% from spinach and orange. Most pesticides were recovered in the range 70-115% with RSD usually < 10% for five experiments. The residue analyses were performed by the extraction of 12 pesticides from 13 samples. The two methods resulted in similar residue levels except chlorothalonil in celery, for which the result was lower with the proposed method. The results confirmed that the proposed method could be applied to monitoring of pesticide residue in foods.

Inhalation and dietary exposure to Dechlorane Plus and polybrominated diphenyl ethers in Osaka, Japan.

This study estimated daily exposure to Dechlorane Plus (DP) and polybrominated diphenyl ethers (PBDE) via inhalation and diet. Samples of atmospheric particles and food (obtained by market basket method) from Osaka, Japan were analyzed for DP (syn-, anti-) and PBDE using gas chromatography-mass spectrometry. DP was detected in both atmospheric particles and food samples. Among the atmospheric particles, DP was detected in all samples. ΣDP concentration was 7.1-15.4 pg m(-3) and anti-DP was the dominant residue among DP isomers. PBDE was also detected in all the atmospheric particles. ΣPBDE concentration was 9.9-23.3 pg m(-3). In the market basket study, DP was detected in Groups Ш (sugar and confectionary), V (legumes and their products), X (fish, shellfish, and their products), and XI (meat and eggs) at concentrations of 3.3, 2.8, 1.9, and 1.5 pg g(-1) wet wt, respectively. PBDE was detected in Groups Ш, IV (oils and fats), V, X, XI, and XШ (seasonings and other processed foods) at concentrations of 153, 79.1, 74.6, 308, 94.8, and 186 pg g(-1) wet wt, respectively. The daily intake of ΣDP (750 pg day(-1)) via inhalation and diet was approximately one percent of that for ΣPBDE (62 ng day(-1)).

Multiresidue analysis of pesticides in vegetables and fruits using a high capacity absorbent polymer for water

A single extraction and a single clean-up procedure was developed for multi-residue analysis of pesticides in non-fatty vegetables and fruits. The method involves the use of a high capacity absorbent polymer for water as a drying agent in extraction from wet food samples and of a graphitized carbon column for clean-up. A homogeneously chopped food sample (20 g) and polymer (3 g) were mixed to absorb water from the sample and then 10 min later the mixture was vigorously extracted with ethyl acetate (100 ml). The extract (50 ml), separated by filtration, was loaded on a graphitized carbon column without concentration. Additional ethyl acetate (50 ml) was also eluted and both eluates were concentrated to 5 ml for analysis. The procedure for sample preparation was completed within 2 h. In a recovery test, 107 pesticides were spiked and average recoveries were more than 80% from asparagus, orange, potato and strawberry. Most pesticides were recovered in the range 70-120% with usually less than a 10% RSD for six experiments. The results indicated that a single extraction with ethyl acetate in the presence of polymer can be applied to the monitoring of pesticide residues in foods.

Di(2-ethylhexyl)phthalate and mono(2-ethylhexyl)phthalate in media for in vitro fertilization

In vitro fertilization (IVF) is one of the most important treatments of infertility to provide a chance of conceiving. In IVF treatment, sperm are washed and motile sperm are isolated with sperm washing media (SWM) for the purpose of fertilization; fertilized ova are then incubated for a maximum of 5 or 6d in media for IVF (IVFM). The exposure of fertilized ova to chemicals via such media has not been studied. We determined the concentrations of two contaminants; di(2-ethylhexyl)phthalate (DEHP) and its hydrolyzed product mono(2-ethylhexyl)phthalate (MEHP) in IVFM, SWM, and protein sources (PS: human serum albumin or serum substitute) for IVFM and SWM. The DEHP and MEHP in these media were extracted by a liquid-liquid extraction method and their concentrations determined by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Fifteen IVFM, nine SWM, and six PS obtained in Japan were examined. The concentrations of DEHP and MEHP in IVFM and SWM were <10-114 and <2.0-263 ng mL(-1), respectively. The concentrations of both DEHP and MEHP were higher in the media containing PS than in those without PS. Either MEHP alone or both DEHP and MEHP were detected in PS. The concentrations of DEHP and MEHP in PS were <10-982 and 47.0-1840 ng mL(-1), respectively. The DEHP and MEHP detected in these media were derived from PS. This is the first study on the chemical contamination of IVFM, SWM, and PS.