Determination of nonylphenol ethoxylates and octylphenol ethoxylates in environmental samples using 13C-labeled surrogate compounds

Alkylphenol polyethoxylates (APEOs) have been widely used as nonionic surfactants in a variety of industrial and commercial products. Typical compounds are nonylphenol polyethoxylates (NPEOs) and octylphenol polyethoxylates (OPEOs), which serve as precursors to nonylphenol (NP) and octylphenol (OP), respectively. NP and 4-t-OP are known to have endocrine disrupting effects on fish (medaka, Oryzias latipes), so it is important to know the concentrations of APEOs in the environment. Because the analytical characteristics of these compounds depend on the length of the ethoxy chain, it is necessary to use appropriate compounds as internal standards or surrogates. We synthesized two 13C-labeled surrogate compounds and used these compounds as internal standards to determine NPEOs and OPEOs by high-performance liquid chromatography (LC)-mass spectrometry. Method detection limits were 0.015 microg/L for NP (2)EO to 0.037 microg/L for NP(12)EO, and 0.011 microg/L for OP(3,6)EO to 0.024 microg/L for OP (4)EO. NPEO concentrations in water from a sewage treatment plant were less than 0.05-0.52 microg/L for final effluent and 1.2-15 microg/L for influent. OPEO concentrations were less than 0.05-0.15 microg/L for the final effluent and less than 0.05-1.1 microg/L for influent.     

Recycling process for yttria-stabilized tetragonal zirconia ceramics using a hydrothermal treatment

The recycling process for 3 mol% yttria-stabilized tetragonal zirconia polycrystals (3Y-TZP) sintered at 1450°–1550°C was examined by applying low-temperature degradation of zirconia ceramics under hydrothermal conditions. Hydrothermal treatment at a temperature from 200° to 240°C can lead to the spontaneous disintegration of 3Y-TZP sintered bodies into powdery particles. The hydrothermally obtained zirconia powder was found to consist of primary particles and aggregated particles. Detailed X-ray diffraction measurement revealed the formation of a cubic zirconia phase in the 3Y-TZP sintered bodies, which seemed to inhibit the disintegration of aggregated particles toward the primary particle level. The reclaimed 3Y-TZP powder was sintered again through a conventional powder processing route. The mechanical properties and microstructure of recycled 3Y-TZP sintered specimens were examined by comparison with those of the original 3Y-TZP sintered bodies. Dense recycled 3Y-TZP sintered at a higher temperature exhibited higher fracture toughness to some degree than the original 3Y-TZP.     

Biobased Contents of Organic Fillers and Polycaprolactone Composites with Cellulose Fillers Measured by Accelerator Mass Spectrometry Based on ASTM D6866

The biobased contents of raw materials such as starches, sugar, chitin, or wood powders for biomass plastics were measured using Accelerator Mass Spectrometry (AMS) based on ASTM D6866. AMS measures the isotope carbon ratio of ¹⁴C to ¹²C and ¹³C in graphite derived from sample powders. The biobased contents of starches, sugar or chitin were almost 100% which means that they are fully biobased. The biobased contents of the wood powders were over 140% due to the effect of the post 1950s ¹⁴C injection due to nuclear testing. Poly(ε-caprolactone) (PCL) composite samples were prepared using the polymerization and direct molding method. The starting compound was the ε-caprolactone monomer liquid combined with cellulose and inorganic fillers using aluminum triflate as a catalyst at 80 °C for 6 or 24 h. PCL cylinder-shaped composite samples with a homogeneously dispersed cellulose filler were prepared with M_n = 4,600 (M_w/M_n = 2.9). The biobased content of the PCL composite with 50 wt% cellulose filler (51.67%) measured using AMS was slightly higher than the carbon ratio of cellulose in the starting powder samples (41.3 mol%). This is due to the higher biobased content (112.70%) of the cellulose filler used in this study. The biobased content of the polymer composite powders by AMS was found not to be affected by the presence of inorganic fillers, such as talc.     

Screening of endophytic bacteria against fungal plant pathogens

Bacterial endophytes were found from 6 plant leaves among 35 plant leaves screened. Two of the isolated bacteria showed antagonistic activity against fungal plant pathogens. An isolate named KL1 showed the clear inihibition against plant pathogens, Fusarium oxysporum and Rhizoctonia solani, on PDA as well as TSA plate. Supernatant of the bacterial culture also showed the clear inhibition against the fungal growth on the plate and the antibiotic substance was identified as iturin A by HPLC analysis. KL1 was identified as Bacillus sp. from the 16S rRNA gene analysis. Very thin hyphae of R. solani was miccroscopically observed when the fungus was co-cultivated with KL1.     

Rate of hexabromocyclododecane decomposition and production of brominated polycyclic aromatic hydrocarbons during combustion in a pilot-scale incinerator

Here, we examined the incineration of extruded polystyrene containing hexabromocyclododecane(HBCD) in a pilot-scale incinerator under various combustion temperatures(800–950℃) and flue gas residence times(2–8 sec). Rates of HBCD decomposition ranged from 99.996%(800℃, 2 sec) to 99.9999%(950℃, 8 sec); the decomposition of HBCD, except during the initial stage of combustion(flue gas residence time 2 sec), followed a pseudo-first-order kinetics model. An Arrhenius plot revealed that the activation energy and frequency factor of the decomposition of HBCD by combustion were 14.2 kJ/mol and 1.69 sec~(-1),respectively. During combustion, 11 brominated polycyclic aromatic hydrocarbons(BrPAHs)were detected as unintentional by-products. Of the 11 BrPAHs detected, 2-bromoanthracene and 1-bromopyrene were detected at the highest concentrations. The mutagenic and carcinogenic BrPAHs 1,5-dibromoanthracene and 1-bromopyrene were most frequently detected in the flue gases analyzed. The total concentration of BrPAHs exponentially increased(range,87.8–2,040,000 ng/m~3) with increasing flue gas residence time. Results from a qualitative analysis using gas chromatography/high-resolution mass spectrometry suggest that bromofluorene and bromopyrene(or fluoranthene) congeners were also produced during the combustion.     

High-solids anaerobic mono-digestion of riverbank grass under thermophilic conditions

The purpose of this study was to investigate the potential of high-solids anaerobic mono-digestion of riverbank grass under thermophilic conditions, focusing on the effects of the strength and the amount of inoculum. Ensiled grass was inoculated with three different inocula; inoculum from liquid anaerobic digester (LI), inoculum from dry anaerobic digester (DI), and mixture of LI and DI (MI), at feedstock-to-inoculum ratio (FIR) of 1, 2 and 4. The ensiling process of riverbank grass reduced moisture content (p > 0.05), while the hemicellulose content was significantly increased from 30.88% to 35.15% (p < 0.05), on dry matter basis. The highest methane production was at an FIR of 2 with MI (167 L/kg VS_added), which was significantly higher (p < 0.05) than with DI, but not significant compared to LI (p > 0.05). At an FIR of 4, digesters inoculated with LI and DI failed to produce methane, whereas 135 L_CH4/kg VS_added was obtained with MI. The kinetic studies showed that at an FIR of 1 with LI and MI, the inoculum had less of effects on the hydrolysis rate constant (0.269 day^− 1 and 0.245 day^− 1) and methane production (135 versus 149 L/kg VS_added); rather, it affected the lag phase. In a thermophilic HS-AD of riverbank grass, the mixture of inoculum with low and high total solids content (TS) helps increase the TS of inoculum and digestion process. An FIR of 2 was deducted to be the limit for a better startup time and higher volumetric productivity of methane.     

Accelerated biodegradation of nitrophenols in the rhizosphere of Spirodela polyrrhiza

We investigated the biodegradation of 2-nitrophenol (2-NP), 4-nitrophenol (4-NP), and 2,4-dinitrophenol (2,4-DNP) in the rhizosphere of Spirodela polyrrhiza plants by conducting degradation experiments with three river water samples supplemented with each nitrophenol (NP). We then isolated NP-degrading bacteria both from the S. polyrrhiza roots and from the river water. In the river water samples, removal of the three NP was accelerated in the presence of S. polyrrhiza plants. The three NPs persisted in an autoclaved solution with sterile plants suggests that NP removal was accelerated largely by bacterial NP biodegradation rather than by adsorption and uptake by the plants. We isolated 8 strains of NP-degrading bacteria: 6 strains from the S. polyrrhiza roots and 2 strains from river water without the plants. The 2-NP- and 2,4-DNP-degrading bacteria were isolated only from the S. polyrrhiza roots. The 4-NPdegrading bacteria different from those isolated from the river water samples were also found on S. polyrrhiza roots. The 2-NP- and 4-NP-degrading strains isolated from the roots utilized the corresponding NP (0.5 mmol/L) as the sole carbon and energy source. The 2,4-DNP-degrading strains isolated from the roots showed substantial 2,4-DNP-degrading activity, but the presence of other carbon and energy sources was required for their growth. The isolated NP-degrading bacteria from the roots must have contributed to the accelerated degradation of the three NPs in the rhizosphere of S. polyrrhiza. Our results suggested that rhizoremediation with S. polyrrhiza may be effective for NP-contaminated surface water.     

Investigation on the humification of municipal solid waste incineration residue and its effect on the leaching behavior of dioxins

In this study, we investigated the humification of municipal solid waste incineration residue through identification of extracted humic substances, and examined the leachability of dioxins by batch leaching test. The samples were incineration residues excavated from lysimeters 6-8 years after being filled. The results of investigation of humic substances showed that the top layers from the surface to a depth of 30-70 cm contained more humic substances than the other layers judging from the color of the samples and optical characteristics of the extracts. In particular, humification in the lysimeter filled with a small amount of compost had progressed through all the layers, not only the top one. The tests revealed that the leaching concentrations of dioxins increased with advanced humification and showed relatively good correlation to dissolved organic carbon (DOC) of leachate at each lysimeter. Humification advances from the surface first, and DOC generated from the humification may preferentially carry down the highly chlorinated dioxin compounds such as O8CDD as DOC-dioxin complexes. Comparing the content and leaching concentration according to depth, we observed not only a decrease in dioxin content but also an increase in leaching of the highly chlorinated dioxins at deeper layers in the lysimeters with the compost. This tendency seemed to result from biological activities.     

Disposition of bisphenol A in pregnant mice and fetuses after a single and repeated oral administration

The risk assessment of bisphenol A (BPA) on the development of offspring of humans is an important issue. There have been some reports on the fate of BPA in rodents, but information on the BPA level in fetal organs essential for the extrapolation to humans is inadequate. In the present study, we investigated the distribution pattern of ¹⁴C-BPA-derived radioactivity in fetal tissues following administration of 10?mg/kg ¹⁴C-BPA to the pregnant mice. The radioactivity was rapidly transferred through placenta and distributed to all fetal organs including reproductive organs and brains in a similar level. The concentration declined slowly compared with dams. Analysis of metabolites in fetuses showed that a fraction of BPA was unexpectedly large compared to the maternal blood. There was no clear effect of the fetal position in a uterus to influence the radioactivity concentration in whole fetuses. The dose dependence of pharmacokinetics should be recognized to extrapolate the pharmacokinetic result from animal experiments at high doses to humans at low doses. Similar experiments were conducted with an addition of two doses, 1 and 100?mg/kg, respectively. The pharmacokinetics seemed to be linear between 1 and 10?mg/kg, although at 100?mg/kg BPA was absorbed slowly and the radioactivity concentrations in fetuses were much higher than expected based on the linear dose dependence. Repeated doses were administered to pregnant mice since humans are exposed to BPA chronically. Radioactivity level in most of the fetal tissues on repeated administration was higher than single administration.     

Sustainability and the measurement of future paths in genuine savings: case studies

This paper extrapolates future paths of genuine savings (GS) by using our integrated assessment model. The results with the base case (BC) indicate that both GS without population change (GS) and GS with population change (GSn) are almost positive in OECD countries in the twenty-first century (satisfying the necessary but insufficient condition for sustainability); those numbers are projected to be negative in 2100. Asia (ASIA), the Middle East and Africa (MEAF), the former Soviet Union and Eastern Europe (FSEE), and the world show upward trends for both values, showing negative signs in 2010 and positive signs after 2050 (in ASIA, MEAF, and the world) and in 2100 (in FSEE). The values in Latin America (LAMR) remain negative throughout. We examine additional following three cases: demand reduction (DR), carbon dioxide (CO₂) emissions reduction (CR), and population reduction (PR). The GSn results compared to the BC indicate that (1) GSn in DR is similar to that of BC, (2) GSn in PR is slightly higher than that of BC, and (3) GSn in CR is unexpectedly lower than that of BC. This GSn reduction in the CR case derives from the fact that the term for calculating resource depletion (especially resource rent, which equals the difference between price and cost) in GS and GSn increased, leading to a greater term being subtracted from gross savings. The resource price increases with the marginal price of natural gas, given the energy-source shift in reducing CO₂ emissions, from cheap coal to expensive natural gas.