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.     

Preparation of Cationic/Anionic Chitin Nanofiber Composite Materials

In this study, we investigated the preparation of cationic/anionic chitin nanofiber (CNF) composite materials by electrostatic interaction. An aqueous dispersion of amidinium CNF was prepared by a top-down approach, and a maleylated CNF film was obtained by a bottom-up approach from a chitin ion gel in an ionic liquid with subsequent maleylation on the CNFs. The resulting film was dispersed in ammonia (aq), which was then mixed with the aqueous cationic CNF dispersion to give the composite film. The composition of the two CNFs was evaluated by scanning electron microscopy and X-ray diffraction measurements. Tensile testing results indicated that the mechanical properties of the composites were enhanced with increasing degrees of substitution of the cationic and anionic groups on CNFs, and also when the molar ratio of these groups approached 1:1. The dissociation of the two kinds of CNFs by alkaline treatment of the composite film was achieved, suggesting the presence of an electrostatic interaction among the interactions between them.     

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.     

Changes in water-extractability of soil inorganic phosphate induced by chloride and sulfate salts

GOAL, SCOPE AND BACKGROUND: One of the principal experimental variables which effect the results of phosphorus (P) sorption studies is the ionic composition, in addition to both species and concentrations of the contacting solution. In spite of the realization that ionic species, concentrations and their compositions effect P sorption and/or desorption, most of the salt-related studies are confined to Cl- (anion) in association with different cations. While the knowledge about the comparative response of P to Cl- and SO4(2-) ions was lacking, the current study was conducted to evaluate the comparative effects of anions (in association with cations) on inorganic P release and P fractions in the soil. METHODS: The test soil was amended with livestock compost manure (OP); KH2PO4 (IPk) or Ca(H2PO4)2 (IPc) at a rate of 1ppm. Soil was subjected to one salt and nine subsequent water extractions and different P fractions were measured. Four salt types, NaCl, Na2SO4, KCl and K2SO4, were used at levels of 0.5 M. RESULTS: Irrespective of P sources, P release was substantially increased in the salt-pretreated soil as compared to the non-saline soil. Sulfate salts released more P in subsequent water extractions than Cl-. Phosphorus release decreased for salt types with Na2SO4 > NaCl > K2SO4 > KCl and for P sources with OP approximately IPk > Control (without P application) > IPc, respectively. DISCUSSION: No previous study was found to compare the results of more P release by SO4(2-) than Cl- salt. Most of the previous studies focused on anion sorption capacities, but the mechanism for their adsorption is not fully known. Most of the authors suggested that the mechanisms of SO4(2-) and PO4(3-) adsorption are similar, and that both ions compete for the same sorption sites (Kamprath et al. 1956, Couto et al. 1979, Pasricha and Fox 1993). Although adsorbed SO4(2-) does not compete strongly with PO4(3-), there is likely to be some competition for sorption between these anions which may cause comparatively more P release by SO4(2-) than Cl- salts. Higher P release by Na-saturation could be due to the release of P associated with oxide surfaces or due to dissolution of Ca-P phases (Curtin et al. 1987). CONCLUSIONS: Study clearly showed that not only cations species differ for P desorption capacity, but associated anions also play a vital role in the fate of P under saline environments. Synergetic effects exist between Na and SO4(2-) ions which enhanced the P release. This study has also confirmed the fact that P from organic sources is available as well as from inorganic P sources. However, P release depends more on the type of P source applied than on total P. RECOMMENDATIONS AND PERSPECTIVES: It is highly recommended that more than one anion species must be used in the research plans for evaluating the P response in a saline environment. The results have important implications from the point of view of research, as most of the researchers focus on different cations only for evaluating P response to salts from an environmental point of view. However, our study has made it clear that anions in association with cations differed for their effects on P release.     

Mechanism and Characterization of Polyamide 4 Degradation by <Emphasis Type="Italic">Pseudomonas</Emphasis> sp.

We identified a biodegrading microorganism of polyamide (nylon) 4, a linear polymer of γ-aminobutyric acid (GABA). From activated sludge, the biodegrading bacteria strains of Pseudomonas sp. were isolated and identified by their taxonomic characteristics and nucleotide sequences of 16S rDNA. One strain, ND-11, was grown on a minimal medium containing polyamide 4 (PA4) as the sole carbon source. The strain produced GABA as a degradation intermediate, as identified by analyzing the NMR spectra of degraded products. The culture supernatant of strain ND-11 degraded the emulsified PA4 completely within one day. These results suggest that the ND-11 strain degraded PA4 using its extracellular enzymes to hydrolyze amide bonds.     

Mercury volatilization by the most mercury-resistant bacteria from the seawater of Minamata Bay in various physiological conditions

The volatilization of mercuric chloride (HgCl₂) and methyl mercuric chloride (CH₃HgCl) by the 45 strains (35 Pseudoalteromonas sp., 2 Vibrio sp., 1 Aeromonas sp., and 7 unclassified) of the most mercury-resistant bacteria from Minamata Bay seawater was examined in various physiological conditions. The bacteria could grow and volatilize HgCl₂ in the liquid medium containing 1-10% NaCl. Two Pseudoalteromonas strains could grow and volatilize HgCl₂ at pH levels ranging from 5.0 to 10.0. The resting cells of 43 strains could volatilize HgCl₂ at concentrations ranging from 30 to 68% after 1-h incubation at 30vv°C. The resting cells of 41 strains could volatilize CH₃HgCl at concentrations ranging from 13 to 88% after 1-h incubation at 30vv°C. Ninety-two percent of mercury was removed from the phosphate buffer containing 0.1 7g/ml by a resting cell of Pseudoalteromonas strain H-4 after 30-min incubation at 30vv°C. We were able to screen the special bacteria, which could volatilize mercury compounds at a high rate in various physiological conditions, for the purpose of developing mercury removal methods using bacteria.     

Mid–trimester hyperechogenic bowel in a fetus of Japanese origin carrying a new mutation of CFTR gene (L548Q)

We present a case of a fetus with hyperechogenic bowel, in which the L548Q mutation was detected in the mother of Japanese origin and the ΔF508 mutation in the father of Caucasian origin. The fetus proved to be compound heterozygous. Research into cystic fibrosis transmembrane conductance regulator (CFTR) mutations in this case was triggered by the fact that the fetus had a characteristic hyperechogenic bowel image with normal karyotype and no indications of intrauterine infections. Hyperechogenic bowel is highly indicative of a CFTR gene mutation. The incidence of cystic fibrosis (CF) in fetuses with mid-trimester hyperechogenic bowel is 5%, but once the most frequent mutations have been accounted for, rarer mutations must be investigated. Copyright © 2006 John Wiley & Sons, Ltd.     

Electrochemical behaviors of sulfhydryl compounds in the presence of elemental mercury

In the expression of bioaccumulated elemental mercury (Hg 0) toxicity, the first Hg 0 oxidation step is crucial. Therefore, to clarify the mechanism underlying the interactions of sulfhydryl (SH) compounds and Hg 0 in the present study, we analyzed the oxidation of reduced glutathione (GSH) and L-cysteine (Cys) in the presence of Hg 0 in aqueous solution by cyclic voltammetry (CV). Production of Hg2+ in the reaction mixture was found to increase along with a decrease in free SH residues. CV showed that the oxidation of Cys increased after a 4-h incubation in the presence of Hg(0), but the oxidation of Cys after a 24-h incubation was suppressed. Conversely, GSH oxidation increased with incubation time in the absence of Hg(0). In the presence of Hg(0), the oxidation of GSH was suppressed. The different reactivities of Cys and GSH with Hg(0) may arise from differences in their oxidation/reduction potentials and pH. The important SH compound interactions with Hg(0) oxidation were as follows: (i) oxidation of Hg(0) to form either mercurous ion (Hg+) or mercuric ion (Hg2+) which both form stable complexes in aqueous solution as Hg I (RS) or Hg II(RS)2; (ii) catalyzed oxidation of SH compounds in the presence of Hg 0; and (iii) suppression of the oxidation of SH compounds due to the reduced concentration of free SH compounds through the binding of SH compounds with Hg+ or Hg2+ The present results demonstrate the chemical reaction processes by which Hg 0 dissolves in aqueous solution in the presence of SH compounds, and contribute to our understanding of SH compounds in non-enzymatic Hg 0 oxidation in vivo.     

Delignification of disposable wooden chopsticks waste for fermentative hydrogen production by an enriched culture from a hot spring

Hydrogen(H2) production from lignocellulosic materials may be enhanced by removing lignin and increasing the porosity of the material prior to enzymatic hydrolysis. Alkaline pretreatment conditions,used to delignify disposable wooden chopsticks(DWC) waste, were investigated. The effects of NaOH concentration, temperature and retention time were examined and it was found that retention time had no effect on lignin removal or carbohydrate released in enzymatic hydrolysate. The highest percentage of lignin removal(41%) was obtained with 2% NaOH at 100℃, correlated with the highest carbohydrate released(67 mg/gpretreated DWC) in the hydrolysate. An enriched culture from a hot spring was used as inoculum for fermentative H2 production, and its optimum initial pH and temperature were determined to be 7.0 and 50℃, respectively. Furthermore, enzymatic hydrolysate from pretreated DWC was successfully demonstrated as a substrate for fermentative H2 production by the enriched culture. The maximum H2 yield and production rate were achieved at 195 mL H2/g total sugarsconsumedand 116 mL H2/(L·day), respectively.     

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.