Takashi Tomiyasu

Selective determination method for measurement of nitrite and nitrate in water samples using high-performance liquid chromatography with post-column photochemical reaction and chemiluminescence detection

A simple, sensitive and selective method for the simultaneous determination of nitrite and nitrate in water samples has been developed. The method is based on ion-exchange separation, online photochemical reaction, and luminol chemiluminescence detection. The separation of nitrite and nitrate was achieved using an anion-exchange column with a 20mM borate buffer (pH 10.0). After the separation, these ions were converted to peroxynitrite by online UV irradiation using a low-pressure mercury lamp and then mixed with a luminol solution prepared with carbonate buffer (pH 10.0). The calibration graphs of the nitrite and nitrate were linear in the range from 2.0 x 10(-9) to 2.5 x 10(-6)M and 2.0 x 10(-8) to 2.5 x 10(-5)M, respectively. Since the sensitivity of nitrite was about 10 times higher than that of nitrate, the simultaneous determination of nitrite and nitrate in the water samples could be efficiently achieved. This method was successfully applied to various water samples--river water, pond water, rain water, commercial mineral water, and tap water--with only filtration and dilution steps.

Mercury contamination in the Yatsushiro Sea, south-western Japan: spatial variations of mercury in sediment

Mercury-contaminated effluent was discharged into Minamata Bay from a chemical plant over a 20-year period until 1965 (from 1958 to 1959, effluent was discharged into Minamata River), causing Minamata disease. In an effort to characterize the extent of the contamination in the Yatsushiro Sea, the vertical and horizontal distributions of mercury in sediment were investigated. Sediment was sampled at 62 locations in the southern part of the sea from 4 to 6 March 1996. In the lower layers of the long cores of sediment, the total amount of mercury was at a relatively uniform low concentration. We interpret these low values to represent the background concentration absent of anthropogenic influence. The background value thus estimated for the Yatsushiro Sea was 0.059 +/- 0.013 mg kg(-1) (mean +/- S.D., n = 51). The highest concentration in each sample ranged from 0.086 to 3.46 mg kg(-1) (mean, 0.57 mg kg(-1)). The higher values were obtained at stations near Minamata Bay and the Minamata River (the sources of the pollution). Concentrations decreased with distance from the source. An inspection of the vertical profiles of mercury concentration in cores suggested that the deposited mercury had not been fixed in sediment but had been transported, despite 30 years having past since the last discharge of contaminated effluent. At nine stations, extractable inorganic and organic mercury concentrations were determined differentially. Inorganic mercury is the predominant species in sediment and organic mercury comprising approximately 1% of the total.

Highly sensitive method for determination of N-nitrosamines using high-performance liquid chromatography with online UV irradiation and luminol chemiluminescence detection.

A new method for the measurement of N-nitrosamines in part-per-trillion concentrations from water samples without preconcentration steps has been developed. This method is based on online UV irradiation after high-performance liquid chromatographic separation and subsequent luminol chemiluminescence detection without addition of an oxidant. It was confirmed that N-nitrosamines in basic aqueous solution were transformed to peroxynitrite by UV irradiation. The detection limits for this method were 1.5 ng/L, 2.9 ng/L, 3.0 ng/L, and 2.7 ng/L for N-nitrosodimethylamine, N-nitrosomorpholine, N-nitrosomethylethylamine, and N-nitrosopyrrolidine, respectively, at a signal-to-noise ratio of 3. The calibration graphs were linear in the range of 5-1000 ng/L for these N-nitrosamines. This method was used for the determination of N-nitrosamines in tap water, river water, and industrial plant effluent samples. The recoveries of N-nitrosodimethylamine, N-nitrosomorpholine, N-nitrosomethylethylamine, and N-nitrosopyrrolidine present in tap water sample at a concentration of 10 ng/L (mean+/-standard deviation, n=4) were (94.8+/-2.7)%, (102.0+/-6.9)%, (99.3+/-3.9)%, and (102.8+/-2.5)%, respectively. These results indicate that our proposed method can be applied satisfactorily to the determination of N-nitrosamines in water samples.

Vertical variations in the concentration of mercury in soils around Sakurajima Volcano, Southern Kyushu, Japan

In an effort to estimate the influence of mercury emitted from Sakurajima Volcano, Southern Kyushu, Japan, on the accumulation of mercury in soil, the vertical distribution of total mercury in soils was investigated together with organic matter content and grain size. The soils were sampled at a thickness of 1 cm from the surface to depth of 1 m at five locations on Sakurajima and two control locations, i.e. Takatoge approximately 11 km southeast and Suzuyama 22 km southwest of the volcano. The concentration in soils increased with the distance from the volcano and was 6.5+/-1.9 ngg(-1) (n=335), 29.0+/-15.6 ngg(-1) (n=100) and 229+/-105 ngg(-1) (n=103) for Sakurajima, Takatoge and Suzuyama, respectively. The concentration of mercury correlated with the amount of organic matter, but not with grain size distribution. The sedimentation rate for Sakurajima, Takatoge and Suzuyama was estimated from geological data to be approximately 1.3, 0.083 and 0.0048 cmyear(-1), respectively. The relatively fast sedimentation of Sakurajima soil was caused by the frequent precipitation of volcanic ash. The annual deposition of mercury estimated for Sakurajima, Takatoge and Suzuyama from the mercury concentration, sedimentation rate and soil density was 9 x 10(4), 3 x 10(4) and 2 x 10(4) ngm(-2)year(-1), respectively. Although the soil of Sakurajima had the lowest concentration among the three sites, it received the largest amount of mercury.

Bioaccumulation of mercury in a vestimentiferan worm living in Kagoshima Bay, Japan

The present study reports on the mercury concentrations of the vestimentiferan worm, Lamellibrachia satsuma, (Annelida: Pogonophora) found near hydrothermal vents at a depth of 80-100 m in the northern parts of Kagoshima Bay. The vestimentiferan worms had total mercury concentrations of 238 ng/g in the anterior muscle of the body and 164 ng/g in the posterior trophosome. Methylmercury constituted only 7.6% of total mercury detected anteriorly and 16.3% posteriorly. The mean total mercury concentration in filtrated ambient seawater of the worm habitat was 1.1 ng/l. The worm should accumulate mercury in seawater by a one-step into the anterior and posterior parts as 2.2 x 10(%) and 1.5 x 10(5) times those of the filtered ambient seawater, respectively. The bioaccumulation factor of mercury by the worms with only their respiration would be actually larger than that by other marine animals through food webs. The high bioaccumulation factor of mercury in the worms suggest the following two possibilities: (i) the biological half-life of organomercury in the worm could be exceptionally long; or (ii) the lifetime of vestimentiferan worms examined in the present study could be extremely long. Various metals in one specimen of the worm were analyzed by using ICP-MS, and then gold as well as silver were detected in the worm. Gold was detected for the first time from marine animals.

Background levels of atmospheric mercury in Kagoshima City, and influence of mercury emission from Sakurajima Volcano, Southern Kyushu, Japan

Vapor phase mercury concentration was determined daily for 1 year (Jan. 1996-Jan. 1997) in order to present the levels of atmospheric mercury in Kagoshima City and to estimate the influence of mercury emission from Sakurajima Volcano, southern Kyushu, Japan. The atmospheric mercury was collected on a porous gold collector at Kagoshima University and was determined by cold vapor atomic absorption spectrometry; Kagoshima University of Kagoshima City is located approximately 11 km west of Sakurajima Volcano. The mercury concentration obtained was in the range 1.2-52.5 ng m(-3) (mean 10.8 ng m(-3), n = 169). The atmospheric concentration varied from season to season; the concentration was high in summer and lower in winter. A linear relation was obtained by plotting ln[Hg/ng m(-3)] vs. 1/T for the north, south and west winds with correlation coefficients of -0.76, -0.79 and -0.83, respectively, but no such dependency was found for the east wind (r = -0.035). When the wind is blowing from the east, Kagoshima City is on the leeward side of the volcano. The impact of the fumarolic activity of the volcano on ambient air in the city was evident in the disappearance of temperature dependency with the appearance of the east wind. Atmospheric mercury concentration except for the east wind was considered to be background levels of Kagoshima City. As background levels, 8.1 +/- 5.3 ng m(-3), 14.8 +/- 7.9 ng m(-3), 13.9 +/- 11.7 ng m(-3) and 4.4 +/- 1.6 ng m(-3) (mean +/- S.D.) were obtained for spring, summer, autumn and winter, respectively.

The distribution of mercury around the small-scale gold mining area along the Cikaniki river, Bogor, Indonesia.

The distribution of mercury in the soil, sediment and river water around the artisanal small-scale gold mining (ASGM) area along the Cikaniki River, West Java, Indonesia, was investigated. The total mercury concentration (T-Hg) in the forest soil ranged from 0.11 to 7.0mgkg(-1), and the highest value was observed at the ASGM village. In the vertical T-Hg profile around the villages, the highest value was observed at the soil surface, and the concentration decreased with depth. This result suggested that the mercury released by mining activity was dispersed through the atmosphere and deposited on the surface. The total organic carbon content (TOC) showed a similar vertical profile as the T-Hg, and a linear relationship was found between T-Hg and TOC. Mercury deposited on the surface can be absorbed by organic matter. The slope of the line was larger near the ASGM village, implying a higher rate of deposition of mercury. The T-Hg in the sediment ranged from 10 to 70mgkg(-1), decreasing gradually toward the lower reaches of the river. Mining waste can be transported with the river flow and deposited along the river. The distribution of the mining waste can be determined using the mineralogical composition measured by X-ray fluorescence spectrometry.

Detection of localized methylmercury contamination by use of the mussel adductor muscle in Minamata Bay and Kagoshima Bay, Japan.

Based on our previous finding that the concentrations of total mercury in mussel adductor muscle approximated those of methylmercury, we compared concentrations of total mercury in the adductor muscle of the mussel Mytilus galloprovincialis, collected from four sites around Minamata City from 1993 to 1995 and four sites in Kagoshima Bay from 1997 to 1998, to assess the level of localized methylmercury contamination. Though the input of mercury from the chemical plant had stopped by around 1970, concentrations of total mercury in the mussel adductor muscle were higher at two sites (26-121 ng/g, n = 135) near the main fallout of wastewater from the chemical plant in Minamata Bay than at the other sites, i.e. two sites 1-5 km from the former sites in Minamata City (6-28 ng/g, n = 52), and all sites in Kagoshima Bay (2-30 ng/g, n = 287). The localized methylmercury contamination around the chemical plant in Minamata Bay was documented also by our sensitive analysis of mercury concentrations in seawater and sediment samples. The survey of concentrations of total mercury in the mussel adductor muscle seems to be useful for monitoring the methylmercury contamination in coastal areas.

A pH Scale for the Protic Ionic Liquid Ethylammonium Nitrate

To quantify the properties of protic ionic liquids (PILs) as acid-base reaction media, potentiometric titrations were carried out in a neat PIL, ethylammonium nitrate (EAN). A linear relationship was found between the 14 pKa  values of 12 compounds in EAN and in water. In other words, the pKa  value in EAN was found to be roughly one unit greater than that in water regardless of the charge and hydrophobicity of the compounds. It is possible that this could be explained by the stronger acidity of HNO3 in EAN than that of H3 O(+) in water and not by the difference in the solvation state of the ions. The pH value in EAN ranges from -1 to 9 on the pH scale based on the pH value in water.

Kinetic spectrophotometric determination of traces of tungsten(VI) by the catalytic reaction of chlorpromazine with hydrogen peroxide. A mechanistic study

A catalytic spectrophotometric method for the determination of traces of tungsten(VI) is proposed. Chlorpromazine (CP) is oxidized by hydrogen peroxide to form a colorless sulfoxide. The reaction is accelerated by trace amounts of tungsten(VI) and can be followed by measuring the increase in absorbance at 344 nm. Since the initial slope R0 of the absorbance/time curves increases with an increase in the tungsten(VI) concentration, R0 is used as the parameter for tungsten(VI) determination. Under the optimum experimental conditions (8.2 × 10−4 M chlorpromazine, 0.42 M sulfuric acid, 0.010 M hydrogen peroxide, 40 °C), tungsten(VI) can be determined in the range 2 μg 1−1–10 mg 1−1. The relative standard deviations are 0.8, 6.0 and 6.8% for 60, 10 and 5 μg 1−1, respectively. This method was successfully applied to a determination of tungsten(VI) in hot spring water samples. According to results of a kinetic study, a mechanism is proposed which leads to the following rate equation: Rcat0 = ([W(VI)][H+][H2O2]2[CP] + [W(VI)][H+]2[H2O2]2[CP])(P + Q[H+] + S[H+][H2O2] + T[H+][H2O2]2).