Studies on automated survey system of environmental chemicals by gas chromatography-mass spectrometry-computer I. Retrieval system of mass spectra

A retrieval system of mass spectra based upon the Probability Based Matching method was studied in order to apply it to survey the chemicals in environments by a gas chromatography-mass spectrometry-computer system. As retrieval indices, peak missing probability and relative confidence value were proposed.     

Three-dimensional diffusion of non-sorbing species in porous sandstone: computer simulation based on X-ray microtomography using synchrotron radiation

The diffusion pathways of porous sandstone were examined by a three-dimensional (3-D) imaging technique based on X-ray computed tomography (CT) using the SPring-8 (Super Photon ring-8 GeV, Hyogo, Japan) synchrotron radiation facility. The analysis was undertaken to develop better understanding of the diffusion pathways in natural rock as a key factor in clarifying the detailed mechanism of the diffusion of radionuclides and water molecules through the pore spaces of natural barriers in underground nuclear waste disposal facilities. A cylindrical sample (diameter 4 mm, length 6 mm) of sandstone (porosity 0.14) was imaged to obtain a 3-D image set of 450(3) voxels=2.62(3) mm(3). Through cluster-labeling analysis of the 3-D image set, it was revealed that 89% of the pore space forms a single large pore-cluster responsible for macroscopic diffusive transport, while only 11% of the pore space is made up of isolated pores that are not involved in long-range diffusive transport. Computer simulations of the 3-D diffusion of non-sorbing random walkers in the largest pore cluster were performed to calculate the surface-to-volume ratio of the pore, tortuosity (diffusion coefficient in free space divided by that in porous rock). The results showed that (i) the simulated surface-to-volume ratio is about 60% of the results obtained by conventional pulsed-field-gradient proton nuclear magnetic resonance (NMR) laboratory experiments and (ii) the simulated tortuosity is five to seven times larger than the results of laboratory diffusion experiments using non-sorbing I(-) and Br(-). These discrepancies are probably attributed to the intrinsic sample heterogeneity and limited spatial resolution of the CT system. The permeability was also estimated based on the NMR diffusometry theory using the results of the random walk simulations via the Kozeny-Carman equation. The estimated permeability involved an error of about 20% compared with the permeability measured by the conventional method, suggesting that the diffusometry-based NMR well logging with gradient coils is applicable to the in-situ permeability measurement of strata. The present study demonstrated that X-ray CT using synchrotron radiation is a powerful tool for obtaining 3-D pore structure images without the beam-hardening artifacts inevitable in conventional CT using X-ray tubes.     

The effect of copper speciation on the formation of chlorinated aromatics on real municipal solid waste incinerator fly ash

A limited amount of information exists regarding the relationship between the chemical form of copper and the formation of chlorinated aromatics in fly ash. To understand the effects of the various forms of copper on the formation of chlorinated aromatics in real fly ash, we determined the chemical forms of copper present in various types of real fly ash using X-ray absorption near edge structure (XANES) and evaluated the relationship between the chemical forms of copper and the formation of chlorinated aromatics. Copper chloride hydroxide (CuCl2 x 3Cu(OH)2) and cuprous chloride (CuCl) were the predominant copper species found in real fly ash. Although pure cupric chloride (CuCl2) is known to be the most active catalyst for the formation of chlorinated aromatics under experimental conditions with synthetic fly ash, CuCl2 was not found in every real fly ash sample. The amount of copper chloride hydroxide was positively correlated with the formation of chlorinated aromatics in real fly ash and is, consequently, considered to be one of the key species involved in the formation of chlorinated aromatics.     

Erythrocyte supply from the spleen and hemoconcentration in hypoxic yellowtail

Hematocrit and hemoglobin concentration of yellowtail blood elevated more than 30% during severe hypoxia for 35 or 40 min. About 40% of the hematocrit elevation is considered to have been caused by erythrocyte supply from the spleen, and about 60% by hemoconcentration due to water shift out of the circulating plasma. Osmotic swelling of erythrocytes is considered not to have occurred, judging from the constant level in the saturation index of the blood.     

Transportation of organic matter to the sea floor by carrion falls of the giant jellyfish <Emphasis Type="Italic">Nemopilema nomurai</Emphasis> in the Sea of Japan

The fate of the giant jellyfish Nemopilema nomurai after death was examined in the southwest Sea of Japan. The density of dead jellyfish was greater than that of live animals. The dead animals are heavier than the Japan Sea Proper Water which occurs deeper than 200 m, suggesting that dead jellyfish sink to the sea floor. The sea floor survey, conducted with a towed video tape recorder (VTR) monitoring system between mid September and mid October, observed a total of 138 jellyfish during 28 of 29 operations. The density of carrion ranged between 0.2 and 5.1 individuals/1,000 m² (mean ± SE = 1.1 ± 0.2). Ophiuroids occurred abundantly at 23 jellyfish carcasses and a sea anemone was observed attached to five carcasses. The VTR surveys confirmed that carrion sinks to the sea floor not only during the winter, the normal end of life for medusae, but also during the fall. A trap survey baited with medusae was also employed, and four different species were sampled with the traps: the snow crab (Chionoecetes opilio), a shrimp (Pandalopsis japonica), the ivory shell (Buccinum striatissimum) and an ophiuroid (Ophiura sarsii). Much of the trap bait remained (49–68% weight-mean = 60.3%) during the 23 h soak-time, and the reduction in weight was greater than that observed by bacterial decomposition, suggesting benthic animals consume dead organisms. The present study indicates that dead N. nomurai sink to the sea floor continuously and were subsequently consumed by benthic scavengers.     

Evaluation of river pollution of neonicotinoids in Osaka City (Japan) by LC/MS with dopant-assisted photoionisation

An atmospheric pressure photoionisation (APPI) source for liquid chromatography/mass spectrometry (LC/MS) was applied to determine neonicotinoid pesticides in the aquatic environment. Dopant-assisted APPI was very effective in the ionisation of neonicotinoids. Neonicotinoids generated protonated molecules in APPI with high sensitivity, while adduct ions, such as sodiated molecules, were predominantly generated in conventional electrospray ionisation. The ionisation of neonicotinoids was confirmed by ultra-high-resolution MS. An analytical method coupled with solid phase extraction was developed for acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, and thiamethoxam. Method detection limits were 0.47 to 2.1 ng L(-1) for six neonicotinoids. Dinotefuran was the most frequent and highest among the neonicotinoids examined in the aquatic environment in Osaka, Japan. The maximum concentration of dinotefuran was 220 ng L(-1). Given the toxicity of neonicotinoids for aquatic creatures, the concentrations observed here were substantially low. The change in concentrations was temporally coincident with the period of the neonicotinoid application. Although rapid photodegradation and some degradation products have been elucidated, the degradation products in the aquatic environment were not identified in the present study.     

The effects of pH on fluoxetine in Japanese medaka (Oryzias latipes): acute toxicity in fish larvae and bioaccumulation in juvenile fish

Recent detection of fluoxetine in the aquatic environment and fish suggests a possibly high accumulation of fluoxetine; however, no report is available on the bioaccumulation of fluoxetine in aquatic organisms. Since bioaccumulation of fluoxetine was probably dependent on pH near the pK(a) value of 10.1, experiments were conducted approximately at pH 7, 8, and 9. Distribution coefficients between 1-octanol and water (D(ow)), and those between synthetic membrane vesicles (liposomes) and water (D(lip-wat)) were determined at pH 7, 8, and 9. The D(ow) and D(lip-wat) values increased significantly with increasing pH. Acute toxicity tests were performed using Japanese medaka (Oryzias latipes) prior to the bioaccumulation test, and 96-h LC(50) values were 5.5, 1.3, and 0.20mgl(-1) at pH 7, 8, and 9, respectively. In the bioaccumulation test, concentrations of fluoxetine and its major metabolite, norfluoxetine, in the fish body and liver were measured. The bioconcentration factors (BCF) of fluoxetine for Japanese medaka were 8.8, 3.0x10, and 2.6x10(2) in the body and 3.3x10(2), 5.8x10(2), and 3.1x10(3) in the liver at pH 7, 8, and 9, respectively. The BCF values were lower at pH 7 and higher at pH 9 mainly because of the increase in nonionized species with significantly higher hydrophobicity than the ionized species at pH values closer to pK(a). A similar trend was obtained for the concentration of norfluoxetine in the fish but the pseudo-BCF values (the ratio of the norfluoxetine concentration in the fish and the fluoxetine concentration in test water) were higher than the BCF value of fluoxetine at all pH conditions.     

Composting of food refuse from a student restaurant in Hokkaido University

Over a period of 21 months, we composted food refuse from a student restaurant in Hokkaido University using a commercially available composting machine. The machine had two reactors, each with a working volume of 250 l. The refuse was mixed with sawdust in a ratio of 5 l sawdust to 10 kg refuse, and this mixture was fed into the machine daily. We studied the characteristics of the refuse, the composting mixture, and the finished compost in an effort to optimize the operating parameters. We also evaluated the effectiveness of the composting process by determining the decomposition rates of the composting materials. The optimum moisture content of the composting mixture was between 30% wet basis (wb) and 40% wb in this machine. The composting machine worked well when the first reactor was filled with composting mixture and 0.5 kg lime was added once per week. The mass of the materials supplied was reduced by 84% over the study period. The decomposition rate of the volatile matter in all composting materials was 66%. The mass of the food refuse supplied was 14.8 kg/day on average, and the moisture content of the refuse was 77% wb on average. Received: October 4, 1999 / Accepted: April 4, 2000     

Reaction mechanism and pathway for the hydrothermal electrolysis of organic compounds

In this study, hydrothermal electrolysis experiments using glucose (a biorelated substance) as a starting material were carried out using a specially designed autoclave at 250°C. We could understand the fundamental reaction behavior of glucose under these conditions through various kinds of experiments and product analyses. Another series of experiments using pressurized CO₂ as an electrolyte was conducted to discover whether it is possible to use CO₂ as an alternative electrolyte to the conventional KCl electrolyte, with a view to lowering the environmental impact of the process. It was found that pressurized CO₂ was useful as an environmentally friendly electrolyte, although there were still some problems in terms of the reaction efficiency.     

Properties and biodegradability of chain-extended copoly(succinic anhydride/ethylene oxide)

Chain-extension reactions were carried out using titanium-iso-propoxide (TIP) as a catalyst for a series of polyesters or copolyesterethers with low molecular weights (M _n =1500–10,000) synthesized by the ring-opening copolymerization of succinic anhydride (SA) with ethylene oxide (EO). The copolymers having aM _n from 25,000 to 50,000 of different properties were obtained. Both the melting point (T _m ) and the fusion heat (H), which indicate the crystallinity of the copolymers, rose with an increase in SA content in the copolymers. Semitransparent films were prepared by compression molding of the copolymers. The biodegradation of the copolymer films was evaluated by enzymatic hydrolysis by lipases and by an aerobic gas evolution test in standard activated sludge. The hydrolyzability of these copolymers by three kinds of lipases was affected by their copolymer composition SA/EO, form, andM _n . The copolyesterether (SA/EO=43/57,M _n =48,900) was more easily biodegraded by standard activated sludge compared to the polyester (SA/EO=47/53,M _n =36,300).Presented at the Pacifichem-95, December 17–22, 1995, Honolulu, Hawaii.