Estimation of 1999-2004 dietary daily intake of PCDDs, PCDFs and dioxin-like PCBs by a total diet study in metropolitan Tokyo, Japan

A study of the dietary intake of dioxins, consisting of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) through foods retailed in the metropolitan Tokyo area from 1999 to 2004 was carried out by the total diet-market basket method on the basis of food classification (14 groups) and the data on food consumption in the Tokyo region obtained from the Japan Nutrition Survey. The daily intake of dioxins per kg of body weight for a 50 kg average adult body was 2.18 pg TEQ/kg/day in 1999, 1.87 pg TEQ/kg/day in 2000, 1.25 pg TEQ/kg/day in 2001, 1.60 pg TEQ/kg/day in 2002 and 2003 and 1.55 pg TEQ/kg/day in 2004, respectively. These amounts were less than the tolerable daily intake (TDI) of 4 pg TEQ/kg/day for dioxins established in Japan. The dioxins taken daily through fish and shellfish (group 10) accounted for more than 50% of sum WHO-TEQs. In addition, more than 90% of the daily intake of dioxins was taken through fish and shellfish (group 10), meat and eggs (group 11), milk and dairy products (group 12). Also, this study clearly showed that the ratio of dioxin-like PCBs in the daily intake of dioxins was increasing yearly because the reduction rate of dioxin-like PCBs was lower than that of PCDDs and PCDFs in foods.     

Remazol Brilliant Blue R decolourization by the laccase from Trametes trogii

The decolourization of the recalcitrant dye RBBR by the culture filtrate of Trametes trogii and its isolated laccase was investigated. Both filtrates from Cu-induced cultures as well as purified laccase decolourized the dye RBBR. The purified laccase decolourized the dye down to 97% of 100 mg l(-1) initial concentration of RBBR when only 0.2U ml(-1) of laccase was used in the reaction mixture. The effects of different physicochemical parameters were tested and optimal decolourization rates occurred at pH 5 and at a temperature of 50 degrees C. Decolourization of RBBR occurred in the presence of metal ions which could be found in textile industry effluents. Of all the metal ions tested, FeCl2 was the most inhibiting for the decolourization. HBT was shown to have no effect on the decolourization of RBBR at low concentration, while at a concentration of 5 mM it slightly inhibited decolourization. The presence of aromatic compounds was found to be inhibiting for the decolourization at a concentration of 10 mM, but not at 0.1 mM, while at 1 mM only ortho-diphenols were inhibiting. Probing the effect of methanol it was found that higher concentrations caused a decrease in the decolourization rate of RBBR. The effect of laccase inhibitors on the decolourization of RBBR was tested with L-cysteine, SDS and EDTA. It was demonstrated that L-cysteine was the most inhibiting substrate for the decolourization while SDS was only inhibiting at 10 mM concentration and ETDA was not inhibiting at all tested concentrations.     

Removal of estrogenic activity of natural steroidal hormone estrone by ligninolytic enzymes from white rot fungi

Natural steroidal hormone estrone (E1) was treated with the white rot fungus Phanerochaete sordida YK-624 under ligninolytic condition with low-nitrogen and high-carbon culture medium. E1 decreased by 98% after 5 d of treatment and the activities of ligninolytic enzymes, manganese peroxidase (MnP) and laccase, were detected during treatment, which suggested that the disappearance of E1 is related to ligninolytic enzymes produced extracellularly by white rot fungus. Therefore, E1 was treated with MnP and laccase prepared from the culture of white rot fungi. HPLC analysis demonstrated that E1 disappeared completely in the reaction mixture after 1 h of treatment with either MnP or laccase. Using the yeast two-hybrid assay system, it was also confirmed that both enzymatic treatments completely removed the estrogenic activity of E1 after 2 h. These results strongly suggest that ligninolytic enzymes are effective in removing the estrogenic activity of E1.     

Polycyclic aromatic hydrocarbons (PAHs) in the aerosol in Beijing, China, measured by aminopropylsilane chemically-bonded stationary-phase column chromatography and HPLC/fluorescence detection

We developed a useful analytical method for the determination of polycyclic aromatic hydrocarbons (PAH) concentrations in the aerosol of China. We used an accelerated solvent extraction (ASE) method for the extraction of PAHs from the aerosol samples, in order to reduce the extraction time and the solvent volume used. The optimum purification method was developed, with aminopropylsilane chemically-bonded stationary-phase column chromatography, in order to remove many co-extractives which cannot be removed by conventional purification methods using silica-gel column chromatography. HPLC/fluorescence detection (FLD) was adopted as the analytical method, because it has very high sensitivity to PAH and it is easy to install, operate, and maintain as compared with GC/MS. With the analytical method developed in this study, the recovery and precision (RSD) for most of the PAHs ranged from 75% to 129% and from 2.8% to 22.7%, respectively. The concentrations of PAHs in the aerosol samples collected from October 2003 to April 2005 in Beijing, China were determined using the newly developed method. SigmaPAHs, which is the sum of the concentrations of all detected PAHs, was 177.8 +/- 239.9 ng m(-3) (n = 64). The SigmaPAHs concentration in the heating season (305.1 +/- 279.0 ng m(-3), n = 33) was 7.2 times higher than that in the non-heating season (42.3 +/- 32.0 ng m(-3), n = 31). These strong seasonal variations in atmospheric PAH concentration are possibly due to coal combustion for residential heating in winter.     

Passive sampler derived air concentrations of PBDEs along an urban-rural transect: spatial and temporal trends

Passive air samplers consisting of polyurethane foam (PUF) disks housed in chambers were deployed at several sites along a approximately 75 km urban-rural gradient in Toronto and analyzed for polybrominated diphenyl ethers (PBDEs). Samplers were allowed to integrate gas-phase PBDEs over three consecutive seasons starting in the summer of 2000. PBDEs were fairly uniform along the transect with air concentrations in Toronto (10-30 pgm(-3)) about a factor of two greater than at rural sites. Lowest concentrations were observed during the winter and probably associated with reduced inputs from indoor sources of PBDEs and to a preference for PBDEs to partition to the particle-phase at colder temperatures. The composition of PBDEs in the air samples did not differ across the transect or for the different seasons.     

Geochemical variations in aeolian mineral particles from the Sahara-Sahel Dust Corridor

The Sahara-Sahel Dust Corridor runs from Chad to Mauritania and expels huge amounts of mineral aerosols into the Atlantic Ocean. Data on samples collected from Algeria, Chad, Niger, and Western Sahara illustrate how corridor dust mineralogy and chemistry relate to geological source and weathering/transport history. Dusts sourced directly from igneous and metamorphic massifs are geochemically immature, retaining soluble cations (e.g., K, Na, Rb, Sr) and accessory minerals containing HFSE (e.g., Zr, Hf, U, Th) and REE. In contrast, silicate dust chemistry in desert basins (e.g., Bodélé Depression) is influenced by a longer history of transport, physical winnowing (e.g., loss of Zr, Hf, Th), chemical leaching (e.g., loss of Na, K, Rb), and mixing with intrabasinal materials such as diatoms and evaporitic salts. Mineral aerosols blown along the corridor by the winter Harmattan winds mix these basinal and basement materials. Dusts blown into the corridor from sub-Saharan Africa during the summer monsoon source from deeply chemically weathered terrains and are therefore likely to be more kaolinitic and stripped of mobile elements (e.g., Na, K, Mg, Ca, LILE), but retain immobile and resistant elements (e.g., Zr, Hf, REE). Finally, dusts blown southwestwards into the corridor from along the Atlantic Coastal Basin will be enriched in carbonate from Mesozoic-Cenozoic marine limestones, depleted in Th, Nb, and Ta, and locally contaminated by uranium-bearing phosphate deposits.     

Identification and estrogenic characterization of impurities in commercial bisphenol A diglycidyl ether (BADGE)

A sample of commercial BADGE was fractioned by HPLC and eight impurities including novel propyl derivatives (2), (5) and (6) were identified by NMR spectrometry, FAB-MS and GC-MS. The estrogenicity, both agonist and antagonist, of fractions containing these impurities was measured with a yeast two-hybrid assay incorporating the human (hER alpha) and a competitive binding assay for hER alpha (ELISA). In the yeast two-hybrid assay, estrogenic antagonist activity was found in two fractions, while estrogenic agonist activity was not found in any. In the ELISA method, the binding affinity to hER alpha was found in three fractions. It is probable that a comprehensive assessment of the estrogenic properties of commercial BADGE, and their implications for human health, will require examination of all its components as described here.     

Chemical and biological oxidative effects of carbon black nanoparticles

Several studies show that ultrafine particles have a larger surface area than coarse particles, thus causing a greater inflammatory response. In this study, we investigated chemical and biological oxidative effects of nanoparticles in vitro. Carbon black (CB) nanoparticles with mean aerodynamic diameters of 14, 56, and 95nm were examined. The innate oxidative capacity of the CB nanoparticles was measured by consumption of dithiothreitol (DTT) in cell-free system. The expression of heme oxygenase-1 (HO-1) in rat alveolar type II epithelial cell line (SV40T2) and alveolar macrophages (AM) exposed to CB nanoparticles was measured by ELISA. DTT consumption of 14nm CB was higher than that of other CB nanoparticles having the same particle weight. However, DTT consumption was directly proportional to the particle surface area. HO-1 protein in SV40T2 cells was significantly increased by the 14nm and 56nm CB, however, 95nm CB did not affect. HO-1 protein in AM was significantly increased by the 14, 56, and 95nm CB. The increase in HO-1 expression was diminished by N-acetyl-l-cysteine (NAC) treatment of each CB nanoparticles before exposure although the difference between the effects of NAC-treated and untreated 14nm CB did not achieve significant. In conclusion, CB nanoparticles have innate oxidative capacity that may be dependent on the surface area. CB nanoparticles can induce oxidative stress in alveolar epithelial cells and AM that is more prominent with smaller particles. The oxidative stress may, at least partially, be mediated by surface function of particles.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in rice plants: possible contaminated pathways

Uptake of dioxins was confirmed in rice plants. We determined (i) dioxin concentrations and isomer profiles in leaf+stem samples of rice plants grown in three soils with different dioxin concentrations and isomer profiles and (ii) temporal changes in dioxin concentrations and isomer profiles in rice grown in a paddy field on which agricultural chemicals containing dioxin impurities had been used in previous years. Principal-component and chemical mass-balance analyses of the data showed that dioxin concentrations and isomer profiles in the rice grown in the different soils were similar, even though the dioxin concentrations and isomer profiles of the soils were different. However, the dioxin concentrations in the rice were influenced by dioxin levels in the atmospheric gas phase. Changes in dioxin levels during the growing period of the rice were also strongly influenced by adhesion of the soil to plant components during the early stage of growth, but gradually the influence of the atmospheric gas phase became predominant. Calculated dietary uptake estimates indicated that, even in rice grown in Japan on soil contaminated with high concentrations of dioxins, the amount of dioxins ingested by humans from rice is extremely small, and the amount of dioxins ingested by livestock from forage rice is similar to that for other forage crops.