Nobutake Nakatani

Transesterification of soybean oil using combusted oyster shell waste as a catalyst

Transesterification of soybean oil catalyzed by combusted oyster shell, which is waste material from shellfish farms, was examined. Powdered oyster shell combusted at a temperature above 700 degrees C, at which point the calcium carbonate of oyster shell transformed to calcium oxide, acted as a catalyst in the transesterification of soybean oil. On the basis of factorial design, the reaction conditions of catalyst concentration and reaction time were optimized in terms of the fatty acid methyl ester concentration expressed as biodiesel purity. Under the optimized reaction conditions of a catalyst concentration and reaction time of 25wt.%. and 5h, respectively, the biodiesel yield, expressed relative to the amount of soybean oil poured into the reaction vial, was more than 70% with high biodiesel purity. These results indicate oyster shell waste combusted at high temperature can be reused in biodiesel production as a catalyst.

Simultaneous spectrophotometric determination of phosphate and silicate ions in river water by using ion-exclusion chromatographic separation and post-column derivatization

The simultaneous spectrophotometric determination of phosphate and silicate ions in river water was examined by using ion-exclusion chromatography and post-column derivatization. Phosphate and silicate ions were separated by the ion-exclusion column packed with a polymethacrylate-based weakly acidic cation-exchange resin in the H(+)-form (TSKgel Super IC-A/C) by using ultra pure water as an eluent. After the post-column derivatization with molybdate and ascorbic acid, so-called molybdenum-blue, both ions were determined simultaneously by spectrophotometry. The effects of sulfuric acid, sodium molybdate and ascorbic acid concentrations and reaction coil length, which have relation to form the reduced complexes of molybdate and ions, on the detector response for phosphate and silicate ions were investigated. Under the optimized conditions (color-forming reactant, 50 mM sulfuric acid-10 mM sodium molybdate; reducing agent, 50 mM ascorbic acid; reaction coil length, 6 m), the calibration curves of phosphate and silicate ions were linear in the range of 50-2000 microg L(-1) as P and 250-10,000 microg L(-1) as Si. This method was successfully applied to water quality monitoring of Kurose-river watershed and it suggested that the effluent from a biological sewage treatment plant was significant source of phosphate ion in Kurose-river water.

Photochemical formation of OH radicals in dew formed on the pine needles at Mt. Gokurakuji

Photochemical formation rates and sources of the hydroxyl (OH) radical were determined in dew water formed on the surface of Japanese red pine (Pinus densiflora) needles of declining (NO2 polluted area) and healthy pine stands at Mt. Gokurakuji located west of Hiroshima city in western Japan. The measured OH radical photoformation rates in dew water (n=10), which were normalized to the rate at midday on May 1 at 34°N, ranged from 0.67 to 5.18 µM h−1 (1M=1mol L−1). The mean value (2.69 µM h−1) was higher than that in dew water collected on a Teflon board and higher than the mean value in rain water published previously. Of the total OH radical formation rate observed in dew water on the pine needles, 16.4 % was estimated to originate from N (III) (NO2− and HNO2) and 24.6 % was estimated to originate from NO3−. There were other sources of OH radical photochemical formation in dew water on the pine needles besides photolysis of NO2− and NO3−.

Measurement of ethylene emission from Japanese red pine (Pinus densiflora) under field conditions in NOx-polluted areas

Emission of ethylene from the needles of Japanese red pine, Pinus densiflora, was measured in air-polluted areas in Hiroshima, Japan. We applied a suitable protocol to determine the rate of ethylene emission from the excised needles. The influence of excision of needles on ethylene emission was not detected during the first 4 h of incubation at 20 degrees C. Ethylene emissions were low in the unpolluted (clean) areas regardless of the altitude or season. The emission of stress ethylene increased with the atmospheric NO2 concentration, suggesting that atmospheric NOx or related substances induced the higher ethylene emission in the polluted areas (near urban and industrial areas). In all cases, 1-year-old needles emitted significantly larger amounts of ethylene than the current needles. Ethylene emission did not increase evenly in the polluted areas, but the frequency of trees emitting high ethylene increased. Therefore, threshold rates for the baseline ethylene emission were proposed.

An evaluation of hydroxyl radical formation in river water and the potential for photodegradation of bisphenol A

The influence of the hydroxyl radical (OH) on the photodegradation of the estrogen-like compound, bisphenol A (BPA), was examined in this study. The formation rate of .OH, normalized to the vernal equinox solar noon condition of Higashi-Hiroshima (34°N) was in the range 0.70–3.25 × 10-10M s-1 in Kurose river water. The total consumption rate constant of .OH in river water ranged from 1.66 to 3.89 × 105 s-1. Based on the photochemical formation rate and the total consumption rate constant of “OH, steady-state .OH concentrations on the order of 3.33–8.35 × 10-16 M were determined. The reaction rate constant for .OH with BPA determined by competition kinetics was found to be 1.55 × 1010M-1 s-1 in water containing nitrate ions that photochemically produced .OH. BPA half-lives due to reaction with .OH ranged from 0.6 to 1.6 days of midday-May sunlight in the Hiroshima prefecture, similar to previously reported values for biodegradation, suggesting that the reaction of BPA with .OH has a significant effect on the fate of BPA in river water.

Needle morphology related to chemical contents in the needles of japanese fir (Abies firma) trees subjected to acidic depositions at MT. Oyama, Eastern Japan

Japanese fir (Abies firma) forests on the urban-facing side ofMt. Oyama, eastern Japan are frequently exposed to acidic depositions. These forests have been declining more severely than those on the mountain-facing side. Chlorophyll, N, Mg, K, Ca, P and Al contents were determined for current, one- and two-year-old needles collected from the crown surfaces of Japanese fir tree forming the forest canopy (ca. 30 m height) on both sides of Mt. Oyama. Needle dry mass per needle area on the urban-facing side was significantly smaller than that on the mountain-facing sides for each needle age class. This result suggests that the development of internal tissues of fir needles on the urban-facing side is defective. N and Chl contents per needle area on the urban-facing side were smaller than those on the mountain-facing sides, indicating that photosynthetic activity per needle area is suppressed in the needles from the urban-facing side. For each needle age class, both area- and mass-based Mg contents were smaller on the urban-facing side than on the mountain-facing side, but mass-based Al contents were greater on the urban-facing side. These results suggest that acidic depositions cause nutritional disorders, which, in turn, leads to decreased needle productivity in the fir trees on the urban-facing side.

Automobile exhaust gas as a source of aqueous phase OH radical in the atmosphere and its effects on physiological status of pine trees.

Free radical generation potential of automobile exhaust gas was examined by measuring hydroxyl (OH) radical photo-formation rates in exhaust gas-scrubbing water. Effects of automobile exhausts on physiological status of Japanese red pine trees (Pinus densiflora Sieb. et Zucc.) were also investigated to elucidate the mechanism how the free radicals derived from exhaust gas damage higher plants. Gasoline and diesel exhaust gases were scrubbed into pure water. Potential photo-formation rates of OH radical in aqueous phase (normalized to sun light intensity of clear sky midday on May 1 at 34°N) for gasoline and diesel cars were ave. 51 and 107 μ Mh⁻¹ m⁻³ of exhaust gas, respectively. Nitrite was a dominant source (ca. 70-90%) of photochemical formation of OH radical in both gasoline and diesel car exhausts. The scrubbed solution of diesel car exhaust gas was sprayed for six times per week to needles of pine tree seedlings in open top chambers. Control, exhaust+mannitol (added as OH radical scavenger), and nitrite+nitrate standard solution (equivalent levels existed in the exhaust gas) were also sprayed. Two months sprays indicated that the sprayed solutions of diesel exhaust and nitrite+nitrate caused a decrease of maximum photosynthetic rate and stomata conductance in pine needles while the control and exhaust+mannitol solution showed no effects on photosynthetic activities of pine needles. These results indicated that OH radicals generated mainly from photolysis of nitrite occurring in the scrubbing solution of exhaust gas are responsible for the decrease of photosynthetic activities of pine needles.

Simultaneous analysis of silicon and boron dissolved in water by combination of electrodialytic salt removal and ion-exclusion chromatography with corona charged aerosol detection

Selective separation and sensitive detection of dissolved silicon and boron (DSi and DB) in aqueous solution was achieved by combining an electrodialytic ion isolation device (EID) as a salt remover, an ion-exclusion chromatography (IEC) column, and a corona charged aerosol detector (CCAD) in sequence. DSi and DB were separated by IEC on the H(+)-form of a cation exchange resin column using pure water eluent. DSi and DB were detected after IEC separation by the CCAD with much greater sensitivity than by conductimetric detection. The five-channel EID, which consisted of anion and cation acceptors, cathode and anode isolators, and a sample channel, removed salt from the sample prior to the IEC-CCAD. DSi and DB were scarcely attracted to the anion accepter in the EID and passed almost quantitatively through the sample channel. Thus, the coupled EID-IEC-CCAD device can isolate DSi and DB from artificial seawater and hot spring water by efficiently removing high concentrations of Cl(-) and SO4(2-) (e.g., 98% and 80% at 0.10molL(-1) each, respectively). The detection limits at a signal-to-noise ratio of 3 were 0.52μmolL(-1) for DSi and 7.1μmolL(-1) for DB. The relative standard deviations (RSD, n=5) of peak areas were 0.12% for DSi and 4.3% for DB.

Utilization of a diol-stationary phase column in ion chromatographic separation of inorganic anions

We describe the ion chromatographic separation of inorganic anions using a diol-stationary phase column (-CH(OH)CH(2)OH; diol-column) without charged functional groups. Anions were separated using acidic eluent as in typical anion-exchange chromatography. The retention volumes of anions on the diol-column increased with increasing H(+) concentration in the eluent. The anion-exchange capacities of diol-columns in the acidic eluent (pH 2.8) were larger than that of zwitterionic stationary phase column but smaller than that of an anion-exchange column. The separation of anions using the diol-column was strongly affected by the interaction of H(+) ions with the diol-functional groups and by the types of the eluents. In particular, the selection of the eluent was very important for controlling the retention time and resolution. Good separation was obtained using a diol-column (HILIC-10) with 5 mM phthalic acid as eluent. The limits of detection at a signal-to-noise ratio of 3 ranged from 1.2 to 2.7 μM with relative standard deviations (RSD, n=5) of 0.04-0.07% for the retention time and 0.4-2.0% for the peak areas. This method was successfully applied to the determination of H(2)PO(4)(-), Cl(-), and NO(3)(-) in a liquid fertilizer sample.

Assessment of the River Water Pollution Levels in Kuantan, Malaysia, Using Ion-Exclusion Chromatographic Data, Water Quality Indices, and Land Usage Patterns

Water qualities of three suburban rivers, namely, Kuantan, Belat, and Galing rivers, in Kuantan, Malaysia, were examined effectively by using ion-exclusion/cation-exchange chromatography with water quality indices and land usage data. Specifically, we have focused on evaluating and grasping the effect of sewage/household wastewater discharged from housing areas in the Kuantan district on the river water quality. Based on this study, the following beneficial information were obtained effectively: (1) the pollution levels in the three rivers (Kuantan River: Classes I–III, Belat River: Classes I–III, and Galing River: Classes I–V) are linked with the urbanization level of the river basin area; (2) differences in the biological reactions in the different pollution level rivers are understood; (3) Galing River is among the most polluted rivers not only in Kuantan but also in the Peninsular Malaysia, owing to poor water treatment of the sewage/household wastewater discharged from the river basin area.