Synthesis of calcium phosphate hydrogel from waste incineration fly ash and its application to fuel cell

Waste incineration fly ash was successfully recycled to calcium phosphate hydrogel, a type of fast proton conductor. The crystallized hydrogel from incineration fly ash had a lower electric conductivity and a lower crystallinity than that from calcium carbonate reagent. However, the difference in electric conductivity between these crystallized hydrogels decreases with temperature. This was due to the presence of potassium in the incineration fly ash. The fuel cell with a membrane electrode assembly (MEA) using the calcium phosphate hydrogel membrane prepared from incineration fly ash was observed to generate electricity. The performance of this fuel cell was almost equal to that of a mixture of K₂CO₃ and CaCO₃ reagents; further, the performance of the former was superior to the fuel cell with a perfluorosulfonic polymer membrane at temperatures greater than approximately 85 °C.     

Characterization of trace elements in chicken and duck litter ash

For safe and sustainable management of poultry litter, it is important to evaluate and understand the chemical forms and concentrations of their constituent trace elements during treatment for disposal. This experiment was carried out to compare changes in metal (Cu, Mn, Zn, Pb and Ni) fractions in chicken and duck litter after incineration at temperatures ranging from 200 to 900 degrees C. The metals were stepwise fractionated into exchangeable, adsorbed, organically bound, carbonate precipitated and residual forms by extracting with 0.5M KNO3, de-ionized water, 0.5M NaOH, 0.05M Na2 EDTA and 4M HNO3, respectively. The content of total metal and other elements (i.e., Ca, Mg and K) were was also determined. Results showed an increasing trend in the total concentrations of metals with increasing temperature with higher amounts in chicken litter ash (CLA) than duck litter ash (DLA). Higher temperatures significantly reduced the levels of H2O-soluble Mn, Zn and Ni and enhanced those of Cu and Pb. The metal fractions extracted by EDTA and HNO3 increased directly with increasing temperature while the fraction extracted with KNO3 and NaOH decreased with ashing. For Cu, Mn, Pb and Ni, the amount extracted varied in the order EDTA>HNO3>NaOH>KNO3>H2O, but the absolute amounts differed between CLA and DLA. Peak concentrations of the total metals were achieved at the highest burning temperature. The amount of H2O soluble Ca and Mg decreased and K increased in both CLA and DLA with temperature. Total and exchangeable forms of cations increased with increasing temperature. Total Ca was highest in DLA, whereas total Mg and K were higher in CLA. This study indicated that incinerating poultry litter before soil application may have mixed effects on the vulnerable metal fractions by increasing or decreasing some fractions, depending on poultry type.     

Humification index of composts originating from three types of woody biomass

Composting is a good method for recycling surplus manure and stabilizing organic matter from biowastes. Compost is used as a soil amendment and recently, for restoration of vegetation in barren areas. We investigated the relationship between the type of woody biomass (using Robinia pseudoacacia, Japanese larch and apple) and the humification index (HI) of the resulting compost. This study evaluated the difference in HI between the three compost types, and the structural features of composts and extracted humic acids (HAs). The HIs for R. pseudoacacia and apple were larger than that for Japanese larch after composting for 11 months. The structural features of the Japanese larch compost were also different from the apple and R. pseudoacacia, with a very high carbon/nitrogen ratio. The average molecular weights and ultraviolet–visible spectra (A600/C) of HAs extracted from composting samples at 0 and 11 months indicate that the humification rate of Japanese larch was slower than that of R. pseudoacacia and apple. During composting, the average molecular weights of apple and R. pseudoacacia decreased, while their A600/C values increased, but the reverse was observed for Japanese larch. The humification rate was found to depend on the type of woody biomass being composted.     

Bioprospecting at former mining sites across Europe: microbial and functional diversity in soils

The planetary importance of microbial function requires urgently that our knowledge and our exploitation ability is extended, therefore every occasion of bioprospecting is welcome. In this work, bioprospecting is presented from the perspective of the UMBRELLA project, whose main goal was to develop an integral approach for remediation of soil influenced by mining activity, by using microorganisms in association with plants. Accordingly, this work relies on the cultivable fraction of microbial biodiversity, native to six mining sites across Europe, different for geographical, climatic and geochemical characteristics but similar for suffering from chronic stress. The comparative analysis of the soil functional diversity, resulting from the metabolic profiling at community level (BIOLOG ECOPlates) and confirmed by the multivariate analysis, separates the six soils in two clusters, identifying soils characterised by low functional diversity and low metabolic activity. The microbial biodiversity falls into four major bacterial phyla: Actinobacteria, Proteobacteria, Firmicutes and Bacteroidetes, including a total of 47 genera and 99 species. In each soil, despite harsh conditions, metabolic capacity of nitrogen fixation and plant growth promotion were quite widespread, and most of the strains showed multiple resistances to heavy metals. At species-level, Shannon’s index (alpha diversity) and Sørensen's Similarity (beta diversity) indicates the sites are indeed diverse. Multivariate analysis of soil chemical factors and biodiversity identifies for each soil well-discriminating chemical factors and species, supporting the assumption that cultured biodiversity from the six mining sites presents, at phylum level, a convergence correlated to soil factors rather than to geographical factors while, at species level, reflects a remarkable local characterisation.     

Evaluation of pressurized liquid extraction for determination of organophosphorus and pyrethroid pesticides in soybean

The purpose of this study was to develop an analytical method for the determination of organophosphorus and pyrethroid pesticides in soybean by pressurized liquid extraction (PLE). Two organic solvents, acetone and acetonitrile, were evaluated as extraction solvents. In both cases, the amount of extract was enhanced with increasing extraction temperature. The extracts obtained using acetonitrile were measured by gas chromatography/mass spectrometry after a cleanup process based on the analytical method for the Japanese Positive List System for Agricultural Chemicals Remaining in Foods. The effect of extraction temperature (range: 40– 130°C) on extraction efficiency was evaluated by a recovery study using 21 organophosphorus pesticides and 10 pyrethroid pesticides as target analytes and acetonitrile as the solvent. The results indicated that at 130°C, some organophosphorus pesticides might be degraded, whereas extraction temperatures between 70°C and 100°C were optimal. Next, a prepared sample containing fenitrothion and permethrin was analyzed. Although the sample was not soaked in water prior to analysis, PLE provided analytical results comparable to those obtained by solvent extraction with homogenization. Therefore, PLE is considered a simple and alternative technique for the extraction of organophosphorus and pyrethroid pesticides in soybean.     

Evaluation of pressurized liquid extraction for the analysis of four pesticides in unpolished rice

The aim of to evaluate efficiency of this study was extraction pressurized liquid extraction (PLE) for the analysis of four pesticides, fthalide, etofenprox, fenitrothion, and isoprothiolane, in unpolished rice by comparing with homogenization as a reference technique. The concentrations of four selected pesticides obtained by PLE with acetonitrile at 130°C for 10 min × 2 cycles were comparable to those by homogenization with water-soaking. The repeatability of the analysis, represented as relative standard deviations (RSDs), were 1.4–3.6% (n = 3) for PLE at 130°C and 1.2–3.8% (n = 3) for homogenization with water-soaking. Recovery yields of surrogates were 75–88% and 87–109% for PLE at 130°C and homogenization with water-soaking, respectively, and these were satisfactory according to the method of positive list. This study suggested that PLE can be applied for the analysis of selected four pesticides in unpolished rice as well as homogenization with water-soaking.     

Hydroxylation of bisphenol A by hyper lignin-degrading fungus Phanerochaete sordida YK-624 under non-ligninolytic condition

Bisphenol A (BPA) is one of the representative compounds of the endocrine disrupting compounds group and the highest volume chemicals produced worldwide. As a result, BPA is often detected in many soil and water environments. In this study, we demonstrated the transformation of BPA from liquid cultures inoculated with hyper lignin-degrading fungus Phanerochaete sordida YK-624. Under non-ligninolytic condition, approximately 80% of BPA was eliminated after 7 d of incubation. High-resolution electrospray ionization mass spectra and nuclear magnetic resonance analyses of a metabolite isolated from the culture supernatant suggested that BPA was metabolized to hydroxy-BPA, 4-(2-(4-hydroxyphenyl)propan-2-yl)benzene-1,2-diol, which has a much lower estrogenic activity than BPA. In addition, we investigated the effect of the cytochrome P450 inhibitor piperonyl butoxide (PB) on the hydroxylation of BPA, markedly lower transformation activity of BPA was observed in cultures containing PB. These results suggest that cytochrome P450 plays an important role in the hydroxylation of BPA by P. sordida YK-624 under non-ligninolytic condition.     

Development of the automated cleanup system for the analysis of PCDDs, PCDFs and DL-PCBs

A new automated cleanup system for the analysis of dioxins (PCDDs, PCDFs and DL-PCBs) has been developed. It was controlled by PLC through the touch-panel. This automated cleanup system can simultaneously treat six samples in 2h, using only about 30 mL of solvent. In this study, the recovery rates of the internal standard added as cleanup spiked were between 70% and 120% in the fly ash sample. The RSDs (relative standard deviations) were below 15%. The shortest analysis time from cleanup to calculation of concentration was approximately 6h. Moreover, this automated cleanup system eliminates personal error in sample preparation and training time for the analyst, and improves the accuracy of the experiment. Additionally, this automated cleanup system allowed rapid analysis and less consumption of organic solvent.     

Evaluation of pressurized liquid extraction for determination of organophosphorus and pyrethroid pesticides in soybean

The purpose of this study was to develop an analytical method for the determination of organophosphorus and pyrethroid pesticides in soybean by pressurized liquid extraction (PLE). Two organic solvents, acetone and acetonitrile, were evaluated as extraction solvents. In both cases, the amount of extract was enhanced with increasing extraction temperature. The extracts obtained using acetonitrile were measured by gas chromatography/mass spectrometry after a cleanup process based on the analytical method for the Japanese Positive List System for Agricultural Chemicals Remaining in Foods. The effect of extraction temperature (range: 40- 130°C) on extraction efficiency was evaluated by a recovery study using 21 organophosphorus pesticides and 10 pyrethroid pesticides as target analytes and acetonitrile as the solvent. The results indicated that at 130°C, some organophosphorus pesticides might be degraded, whereas extraction temperatures between 70°C and 100°C were optimal. Next, a prepared sample containing fenitrothion and permethrin was analyzed. Although the sample was not soaked in water prior to analysis, PLE provided analytical results comparable to those obtained by solvent extraction with homogenization. Therefore, PLE is considered a simple and alternative technique for the extraction of organophosphorus and pyrethroid pesticides in soybean.     

Toxicity test using medaka (Oryzias latipes) early fry and concentrated sample water as an index of aquatic habitat condition

The aim of the present study was to show a relationship between toxicity of 100-fold concentrated water and aquatic habitat conditions. Environmental waters are 100-fold concentrated with solid-phase extraction. Medaka early fry was exposed in these waters for 48 h. The number of death and disorder was counted at 1, 2, 3, 6, 12, 24, and 48 h; toxicity was expressed using inverse median effect time and median lethal time (ET (50)(-1), LT (50)(-1)). Average score per taxon (ASPT) for benthic animals and Index of Biotic Integrity (IBI) for fish were applied as indices of aquatic habitat conditions. The results of toxicity test were compared using ASPT and IBI. The different levels of toxicity were detected in the seawater of Japan. At the Husino River area, toxicity cannot be detected. In rivers, high toxicity appeared at urban districts without sewerage. By Spearman coefficient, the relationship between toxicity and high biochemical oxygen demand (BOD) were obtained. BOD household wastewater contains hydrophobic toxic matters; otherwise, seawater in industrial area does not show clear relationship between toxicity and chemical oxygen demand. Gas chromatography to mass spectrometry simultaneous analysis database may give an answer for the source of toxicity, but further test is required. Ratio of clear stream benthic animal sharply decreased over 0.25 of LT (50)(-1) or 0.5 of ET (50)(-1). Tolerant fish becomes dominant over 0.3 of LT (50)(-1) or 0.5-1.0 of ET (50)(-1). By Pearson product-moment correlation coefficient, correlation coefficient between toxicity and ASPT was obtained at -0.773 (ET (50)(-1)) and -0.742 (LT (50)(-1)) at 1 % level of significance with a high negative correlation. Toxicity (LT (50)(-1) ) has strong correlation with the ratio of tolerant species. By Pearson product-moment correlation coefficient, correlation coefficient between toxicity and IBI obtained were -0.155 (ET (50)(-1)) and -0.190 (LT (50)(-1)) at 1 % level of significance and has a low or no correlation between toxicity and IBI. Even with low toxic environmental waters, toxicity test using 100-fold concentrated and medaka early fly could detect acute toxicity. The detected toxicity seemed to limit the inhabiting aquatic species in the water body.