H and O isotopic differences in typhon and urban-induced heavy rain in Tokyo

Stable isotope ratios of hydrogen and oxygen of water are useful tracers of the hydrological cycle. For example, isotopes monitor the evapotranspiration in vegetated areas, local snow ice processes and stream water flow processes. δ¹⁸O and δD in rainwater reflect the processes of evaporation, condensation and precipitation. Heavy rains thus modify the stable isotope ratio of ground water, stream water and transpiration water vapor. However, the controlling factors of δ¹⁸O and δD are not clear. Here we analyzed the inorganic ion concentration and stable isotope ratio in 38 normal rainwater and 15 heavy rainwater samples were collected in Shinjuku, Tokyo, Japan, during four years from October 2012 to December 2015. Results show a decrease in δ¹⁸O and δD values with the total rainfall amount, thus highlighting the amount effect. δ¹⁸O and δD volume-weighted mean values in typhoon heavy rain were higher than the values estimated from amount effect, whereas δ¹⁸O and δD volume-weighted mean values in urban-induced heavy rain were lower. Typhoon heavy rain has high Na⁺ ratio and stable isotope ratios, while urban-induced heavy rain has low Na⁺ ratio and stable isotope ratio.     

Estrogen equivalent concentration of 13 branched para-nonylphenols in three technical mixtures by isomer-specific determination using their synthetic standards in SIM mode with GC-MS and two new diasteromeric isomers

Thirteen isomers of branched para-nonylphenols (para-NP) in three technical mixtures were isomer-specifically determined using their synthesized standards by SIM of structurally specific ions, m/z 135, 149 or 163 with GC–MS. Of the 13 isomers, four isomers, 4-(2,4-dimethylheptan-4-yl)phenol, 4-(4-methyloctan-4-yl)phenol, 4-(3-ethyl-2-methylhexan-2-yl)phenol (3E22NP) and 4-(2,3-dimethylheptan-2-yl)phenol synthesized for their determinations were first used as standard substances. The 13 isomers in the technical mixtures individually occurred at mass percent portion of more than 2%. The total mass percent portions in the mixtures from Tokyo Chemical Industry (TCI), Aldrich, and Fluka covered with 89 ± 2%, 75 ± 4% and 77 ± 2%, respectively. The abundance of 4-(3,6-dimethylheptan-3-yl)phenol in the three mixtures was the largest with 11.1 ± 2% to 9.9 ± 0.3%, while that of 4-(2-methyloctan-2-yl)phenol was the smallest with 2.9 ± 0.3% to 3.0 ± 0.2%. Additionally, structures of four new isomers of more than 1% portion present in a technical mixture were elucidated as two pairs of diastereomeric isomers: two types of 4-(3,4-dimethylheptan-4-yl)phenol (344NP) and those of 4-(3,4-dimethylheptan-3-yl)phenol (343NP). By estrogenic assay of 13 isomers with yeast estrogen screen system, the activity of 3E22NP was the highest, while that of 4-(3-methyloctan-3-yl)phenol was the least. Their relative activities to that of 3E22NP were individually calculated. Estrogenic equivalent concentrations of the three technical mixtures were predictively evaluated. The ratio of the EEC to the conventional concentration, total mass percent portions of the 13 isomers in technical mixtures were 0.208 for TCI, 0.206 for Aldrich and 0.205 for Fluka. The predicted estrogenic activity of measured concentration of para-NP in technical mixtures was approximately 5-fold greater than the measured estrogen agonist activity.     

Historical and geographical aspects of the increasing perfluorooctanoate and perfluorooctane sulfonate contamination in human serum in Japan

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have recently received attention due to their widespread contamination in the environment, as well as in wildlife and humans. We measured the PFOS and PFOA concentrations in historically recorded human serum samples at an age range between 20 and 59 years collected in Kyoto, 20 persons per each time point (n=100), and also the PFOS and PFOA concentrations in human serum samples at an age range between 20 and 59 years from 10 locations throughout Japan (n=200). The historical samples collected from 1983 to 1999 demonstrated that the PFOA concentrations in males and females from Kyoto have increased 4.4-fold and 4.3-fold at a rate of increase of 0.49 ng/ml/year and 0.42 ng/ml/year, respectively. In contrast, serum concentrations of PFOS reached a plateau in the late 1980s. There are also regional differences in both the PFOS and PFOA serum concentrations. The concentrations in serum [geometric mean (geometric standard deviation)] (ng/ml) in 2003-2004 ranged from 7.6(1.6) in the town of Matsuoka in Fukui prefecture to 27.8(1.6) in Kyoto city, and ranged from 2.3(1.5) in Matsuoka to 14.5(1.3) in Osaka city for PFOS and PFOA, respectively.     

Separation, synthesis and estrogenic activity of 4-nonylphenols: two sets of new diastereomeric isomers in a commercial mixture

Two sets of new diastereomeric 4-nonylphenol (NP) isomers [4-(3,4-dimethylheptan-4-yl)phenol (344NP, NP-J, L) and 4-(3,4-dimethylheptan-3-yl)phenol (343NP, NP-K, P)] were separated from a commercial NP mixture. The mixture of these diastereomers was synthesized at the same time by a single Friedel-Crafts reaction of 3,4-dimethyl-4-heptanol and phenol, and the mixture was separated into individual NPs by HPLC equipped with Hypercarb column. For the first time, in this study the stereostructure-estrogenic activity relationship of NP diastereomers was investigated. The NP isomers (NP-L and NP-P) having the beta-methyl group over the benzene ring were found to be 2-4 times more estrogenic than their diastereomers (NP-J and NP-K). In the case of the other set of diastereomer [4-(3,5-dimethylheptan-3-yl)phenol, (353NP, NP-E, G)] containing gamma-methyl group in the molecule, the gamma-methyl proton signal (delta 0.49) in the more estrogenic isomer (NP-G) also appeared in a higher field than the corresponding methyl signal (delta 0.76) of the less estrogenic isomer (NP-E).     

Determination of ammonium on an integrated microchip with LED-induced fluorescence detection

A simply fabricated microfluidic device integrated with a fluorescence detection system has been developed for on-line determination of ammonium in aqueous samples. A 365-nm light-emitting diode (LED) as an excitation source and a minor band pass filter were mounted into a polydimethylsiloxane (PDMS)-based microchip for the purpose of miniaturization of the entire analytical system. The ammonium sample reacted with o-phthaldialdehyde (OPA) on-chip with sodium sulfite as reducing reagent to produce a fluorescent isoindole derivative, which can emit fluorescence signal at about 425 nm when excited at 365 nm. Effects of pH, flow rate of solutions, concentrations of OPA-reagent, phosphate and sulfite salt were investigated. The calibration curve of ammonium in the range of 0.018-1.8 μupg/mL showed a good linear relationship with R² = 0.9985, and the detection limit was (S/N = 3) 3.6 × 10^-4 μupg/mL. The relative standard deviation was 2.8% (n = 11) by calculating at 0.18 μupg/mL ammonium for repeated detection. The system was applied to determine the ammonium concentration in rain and river waters, even extent to other analytes fluorescence detection by the presented device.     

Measurements of aerosol optical properties in central Tokyo during summertime using cavity ring-down spectroscopy: Comparison with conventional techniques

A highly sensitive cavity ring-down spectrometer (CRDS) was used to monitor the aerosol extinction coefficient at 532 nm. The performance of the spectrometer was evaluated using measurements of nearly monodisperse polystyrene particles with diameters between 150 and 500 nm. By comparing the observed results with those determined using Mie theory, the accuracy of the CRDS instrument was determined to be >97%, while the upper limit for the precision of the instrument was estimated to be 0.6–3.5% (typically 2%), depending on the particle number concentration, which was in the range of 30–2300 particles cm^?3. Simultaneous measurements of the extinction (b_ext), scattering (b_sca) and absorption (b_abs) coefficients of ambient aerosols were performed in central Tokyo from 14 August to 2 September 2007 using the CRDS instrument, two nephelometers and a particle/soot absorption photometer (PSAP), respectively. The value of b_ext measured using the CRDS instrument was compared with the sum of the b_sca and b_abs values measured with a nephelometer and a PSAP, respectively. Good agreement between the b_ext and b_sca + b_abs values was obtained except for data on days when high ozone mixing ratios (>130 ppbv) were observed. During the high-O₃ days, the values for b_sca + b_abs were ～7% larger than the value for b_ext, possibly because the value for b_abs measured by the PSAP was overestimated due to interference from coexisting non-absorbing aerosols such as secondary organic aerosols.     

High (210)Po atmospheric deposition flux in the subtropical coastal area of Japan

Bulk atmospheric deposition fluxes of (210)Po and (210)Pb were measured at three coastal regions of Japan, the Pacific Ocean coastal area of the Japanese mainland (Odawa Bay), the Chinese continental side of Japanese coastal area (Tsuyazaki), and an isolated island near Okinawa (Akajima). Wet and dry fallout collectors were continuously deployed from September 1997 through August 1998 for periods of 3 to 31 days depending on the frequency of precipitation events. Annual (210)Pb deposition fluxes at Odawa Bay (35 degrees N 139 degrees E), Tsuyazaki (33 degrees N 130 degrees E) and Akajima (26 degrees N 127 degrees E) were 73.3+/-8.0, 197+/-35 and 78.5+/-8.0 Bqm(-2)y(-1), respectively. Higher (210)Pb deposition was observed at the Chinese continental side of Japanese coast than at the Pacific Ocean coastal site. The high (210)Pb atmospheric flux at the Chinese continental side coast was thought to be attributable to (222)Rn-rich air-mass transport from the Chinese continent during the winter monsoon. In contrast, the annual (210)Po deposition fluxes at the three study sites were 13.0+/-2.3 (Odawa Bay), 21.9+/-4.4 (Tsuyazaki) and 58.4+/-7.7 (Akajima)Bqm(-2)y(-1), respectively, indicating unusual high (210)Po deposition at Akajima during winter. Anomalous unsupported (210)Po input was observed during summer 1997, suggesting unknown source of (210)Po at this area.     

State of mixture of atmospheric submicrometer black carbon particles and its effect on particulate light absorption

The state of mixture of light-absorbing carbonaceous particles was investigated in relation to light absorption properties using electron microscopic examinations, black carbon (BC) analyses of quartz filter by thermal/optical reflectance (TOR) method, measurements with two continuous light-absorbing photometers at a suburban site of Tsukuba, about 60 km northeast of Tokyo. The volume fraction of water-soluble material (?) in individual particles is important for assessing particulate light-absorbing and/or scattering of atmospheric aerosols. The values of ? in BC particles were evaluated by electron micrographs before and after dialysis (extraction) of water-soluble material. The mass absorption coefficient (MAC in units of m² g^?1) tended to increase with increasing the average ? in BC particles with the radius range of 0.05–0.5 μm. Thus, our results indicate that coatings of water-soluble material around BC particles can enhance the absorption of solar radiation. Moreover, the single scattering albedo (SSA) will increase because a large amount of coating material will scatter more light.     

Gamma-dose rates from terrestrial and Chernobyl radionuclides inside and outside settlements in the Bryansk Region, Russia in 1996-2003

In order to estimate current external gamma doses to the population of the Russian territories contaminated as a result of the Chernobyl accident, absorbed gamma-dose rates in air (DR) were determined at typical urban and suburban locations. The study was performed in the western districts of the Bryansk Region within the areas of 30 settlements (28 villages and 2 towns) with the initial levels of 137Cs deposition ranging from 13 to 4340 kBqm(-2). In the towns, the living areas considered were private one-story wooden and stone houses. DR values were derived from in situ measurements performed with the help of gamma-dosimeters and gamma-spectrometers as well as from the results of soil samples analysis. In the areas under study, the values of DR from terrestrial radionuclides were 25+/-6, 24+/-5, 50+/-10, 32+/-6, 54+/-11, 24+/-8, 20+/-6, 25+/-8, and 18+/-5 nGyh(-1) at locations of kitchen gardens, dirt surfaces, asphalt surfaces, wooden houses, stone houses, grasslands inside settlement, grasslands outside settlement, ploughed fields, and forests, respectively. In 1996-2001, mean normalized (per MBqm(-2) of 137Cs current inventory in soil) values of DR from (137)Cs were 0.41+/-0.07, 0.26+/-0.13, 0.15+/-0.07, 0.10+/-0.05, 0.05+/-0.04, 0.48+/-0.12, 1.04+/-0.22, 0.37+/-0.07, and 1.15+/-0.19 microGyh(-1) at the locations of kitchen gardens, dirt surfaces, asphalt surfaces, wooden houses, stone houses, grasslands inside settlement, grasslands outside settlement, ploughed fields, and forests, respectively. The radiometric data from this work and the values of occupancy factors determined for the Russian population by others were used for the assessments of annual effective doses to three selected groups of rural population. The normalized (per MBqm(-2) 137Cs current ground deposition) external effective doses to adults from 137Cs ranged from 0.66 to 2.27 mSvy(-1) in the years 1996-2001, in accordance with professional activities and structures of living areas. For the areas under study, the average external effective doses from 137Cs were estimated to be in the range of 0.39-1.34 mSvy(-1) in 2001. The average external effective doses from natural radionuclides appeared to be lower than those from the Chernobyl fallout ranging from 0.15 to 0.27 mSvy(-1).