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Department of Urban and Environmental Engineering (Environmental Science and Engineering )This study investigated thermodynamic and microscopic characteristics of various F-gas hydrates to examine the feasibility of gas hydrate-based F-gas separation process and to demonstrate the newly discovered F-gas hydrates. Thermodynamic phase equilibria were measured to determine the thermodynamically stable region of each F-gas hydrate, while powder X-ray diffraction was conducted to identify the gas hydrate crystal structure and lattice parameter. In addition, 13C & 19F NMR and insitu Raman spectroscopy were utilized to confirm the hydrate structure and observe cage-filling guestmolecular behavior. Lastly, the gas and hydrate phase compositions were analyzed via gas chromatography to examine the separation efficiency by gas hydrate formation process. From the experimental results, the thermodynamic stability range of pure CHF3 and CHF3 + N2 gas hydrates demonstrated that CHF3 can be captured in hydrate phase with high separation efficiency, while they form sI hydrate regardless of CHF3 concentrations used in this study. On the other hand, pure C2F6 and C2F6 + N2 gas mixture formed sII hydrates, and since C2F6 + N2 + water system showed an azeotropic behavior at high temperature range, restricting the gas hydrate-based separation process only applicable at specific temperature and pressure range. Lastly, the fundamental thermodynamic and spectroscopic properties of pure NF3 hydrate were obtained to estimate the feasibility for gas hydrate-based separation process. This study also made important discoveries on two F-gases (c-C4F8 and C3F8) which form sH hydrate in presence of suitable guest molecules. Since C3F8 and c-C4F8 molecules have large molecular sizes, those molecules have not been expected to be enclathrated in sI or sII hydrate cages. However, this study discovered that c-C4F8 molecules can be enclathrated in sH large (51268) cages in presence of CH4 as help gas, which was demonstrated through PXRD and 13C NMR spectroscopy. In addition, C3F8 was found to act as a dual hydrate former between sH and sII hydrates according to help gas molecules. Via 13C NMR and Raman spectroscopy, C3F8 was confirmed to form sH hydrate with CH4, while forming sII hydrate in presence of SF6. The discovery of c-C4F8 and C3F8 as sH hydrate former is very meaningful, since there have been no gas-phase sH hydrate former investigated until present. The overall results obtained in this study provide invaluable information of various properties of F-gas hydrates, and are expected to be useful sources for gas hydrate application fields in the future.clos

Ga-doped Pt-Ni Octahedral Nanoparticles as a Highly Active and Durable Electrocatalyst for Oxygen Reduction Reaction

Bimetallic PtNi nanoparticles have been considered as a promising electrocatalyst for oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs) owing to their high catalytic activity. However, under typical fuel cell operating conditions, Ni atoms easily dissolve into the electrolyte, resulting in degradation of the catalyst and the membrane-electrode assembly (MEA). Here, we report gallium-doped PtNi octahedral nanoparticles on a carbon support (Ga-PtNi/C). The Ga-PtNi/C shows high ORR activity, marking an 11.7-fold improvement in the mass activity (1.24 A mgPt-1) and a 17.3-fold improvement in the specific activity (2.53 mA cm-2) compare to the commercial Pt/C (0.106 A mgPt-1 and 0.146 mA cm-2). Density functional theory calculations demonstrate that addition of Ga to octahedral PtNi can cause an increase in the oxygen intermediate binding energy, leading to the enhanced catalytic activity toward ORR. In a voltage-cycling test, the Ga-PtNi/C exhibits superior stability to PtNi/C and the commercial Pt/C, maintaining the initial Ni concentration and octahedral shape of the nanoparticles. Single cell using the Ga-PtNi/C exhibits higher initial performance and durability than those using the PtNi/C and the commercial Pt/C. The majority of the Ga-PtNi nanoparticles well maintain the octahedral shape without agglomeration after the single cell durability test (30,000 cycles). This work demonstrates that the octahedral Ga-PtNi/C can be utilized as a highly active and durable ORR catalyst in practical fuel cell applications

Multiple assessment methods of prenatal exposure to radio frequency radiation from telecommunication in the Mothers and Children’s Environmental Health (MOCEH) study

Objectives: To evaluate prenatal exposure to radiofrequency radiation (RFR) from telecommunication using a mobile phone questionnaire, operator data logs of mobile phone use and a personal exposure meter (PEM). Material and Methods: The study included 1228 mother–infants pairs from the Mothers and Children’s Environmental Health (MOCEH) study – a multicenter prospective cohort study ongoing since 2006, in which participants were enrolled at ≤ 20 weeks of pregnancy, with a follow-up of a child birth and growth to assess the association between prenatal environmental exposure and children’s health. The questionnaire included the average calling frequency per day and the average calling time per day. An EME Spy 100 PEM was used to measure RFR among 269 pregnant women from November 2007 to August 2010. The operators’ log data were obtained from 21 participants. The Spearman’s correlation test was performed to evaluate correlation coefficient and 95% confidence intervals between the mobile phone use information from the questionnaire, operators’ log data, and data recorded by the PEM. Results: The operators’ log data and information from the self-reported questionnaire showed significantly high correlations in the average calling frequency per day (ρ = 0.6, p = 0.004) and average calling time per day (ρ = 0.5, p = 0.02). The correlation between information on the mobile phone use in the self-reported questionnaire and exposure index recorded by the PEM was poor. But correlation between the information of the operators’ log data and exposure index for transmission of mobile communication was significantly high: correlation coefficient (p-value) was 0.44 (0.07) for calling frequency per day, and it was 0.49 (0.04) for calling time per day. Conclusions: The questionnaire information on the mobile phone use showed moderate to high quality. Using multiple methods for exposure assessment might be better than using only one method. Int J Occup Med Environ Health 2016;29(6):959–97

Ga-doped Pt-Ni Octahedral Nanoparticles as a Highly Active and Durable Electrocatalyst for Oxygen Reduction Reaction

Bimetallic PtNi nanoparticles have been considered as a promising electrocatalyst for oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs) owing to their high catalytic activity. However, under typical fuel cell operating conditions, Ni atoms easily dissolve into the electrolyte, resulting in degradation of the catalyst and the membrane-electrode assembly (MEA). Here, we report gallium-doped PtNi octahedral nanoparticles on a carbon support (Ga-PtNi/C). The Ga-PtNi/C shows high ORR activity, marking an 11.7-fold improvement in the mass activity (1.24 A mgPt-1) and a 17.3-fold improvement in the specific activity (2.53 mA cm-2) compare to the commercial Pt/C (0.106 A mgPt-1 and 0.146 mA cm-2). Density functional theory calculations demonstrate that addition of Ga to octahedral PtNi can cause an increase in the oxygen intermediate binding energy, leading to the enhanced catalytic activity toward ORR. In a voltage-cycling test, the Ga-PtNi/C exhibits superior stability to PtNi/C and the commercial Pt/C, maintaining the initial Ni concentration and octahedral shape of the nanoparticles. Single cell using the Ga-PtNi/C exhibits higher initial performance and durability than those using the PtNi/C and the commercial Pt/C. The majority of the Ga-PtNi nanoparticles well maintain the octahedral shape without agglomeration after the single cell durability test (30,000 cycles). This work demonstrates that the octahedral Ga-PtNi/C can be utilized as a highly active and durable ORR catalyst in practical fuel cell applications

Representative levels of blood lead, mercury, and urinary cadmium in youth: Korean Environmental Health Survey in Children and Adolescents (KorEHS-C), 2012–2014

AbstractBackgroundThis study examined levels of blood lead and mercury, and urinary cadmium, and associated sociodemographic factors in 3–18 year-old Korean children and adolescents.Materials and methodsWe used the nationally representative Korean Environmental Health Survey in Children and Adolescents data for 2012–2014 and identified 2388 children and adolescents aged 3–18 years. The median and 95th percentile exposure biomarker levels with 95% confidence intervals (CIs) were calculated. Multivariate regression analyses were performed on log transformed exposure biomarker levels adjusted for age, sex, area, household income, and father’s education level. The median exposure biomarker levels were compared with data from Germany, the US, and Canada, as well as the levels of Korean children measured at different times.ResultsThe median levels of blood lead and mercury, as well as urinary cadmium were 1.23μg/dL, 1.80μg/L, and 0.40μg/L (95% CIs, 1.21–1.25, 1.77–1.83, and 0.39–0.41, respectively). The blood lead levels were significantly higher in boys and younger children (p<0.0001) and children with less educated fathers (p=0.004) after adjusting for covariates. Urinary cadmium level increased with age (p<0.0001). The median levels of blood mercury and urinary cadmium were much higher in Korean children and adolescents than those in their peers in Germany, the US, and Canada. Blood lead levels tended to decrease with increasing age and divergence between the sexes, particularly in the early teen years. Median levels of blood lead and urinary cadmium decreased since 2010.ConclusionSociodemographic factors, including age, sex, and father’s education level were associated with environmental exposure to heavy metals in Korean children and adolescents. These biomonitoring data are valuable for ongoing surveillance of environmental exposure in this vulnerable population

Genetic influences on the onset of obstructive sleep apnoea and daytime sleepiness: a twin study

Background Obstructive sleep apnoea (OSA) is one of the major sources of the excessive daily sleepiness, cognitive dysfunction, and it increases cardiovascular morbidity and mortality. Previous studies suggested a possible genetic influence, based on questionnaires but no objective genetic study was conducted to understand the exact variance underpinned by genetic factors. Methods Seventy-one Hungarian twin pairs involved from the Hungarian Twin Registry (48 monozygotic, MZ and 23 dizygotic, DZ pairs, mean age 51 ± 15 years) underwent overnight polysomnography (Somnoscreen Plus Tele PSG, Somnomedics GMBH, Germany). Apnoea hypopnea index (AHI), respiratory disturbance index (RDI) and oxygen desaturation index (ODI) were registered. Daytime sleepiness was measured with the Epworth Sleepiness Scale (ESS). Bivariate heritability analysis was applied. Results The prevalence of OSA was 41% in our study population. The heritability of the AHI, ODI and RDI ranged between 69% and 83%, while the OSA, defined by an AHI ≥5/h, was itself 73% heritable. The unshared environmental component explained the rest of the variance between 17% and 31%. Daytime sleepiness was mostly determined by the environment, and the variance was influenced in 34% by the additive genetic factors. These associations were present after additional adjustment for body mass index. Conclusion OSA and the indices of OSA severity are heritable, while daytime sleepiness is mostly influenced by environmental factors. Further studies should elucidate whether close relatives of patients with OSA may benefit from early family risk based screening.This study was supported by the Hungarian Pulmonology Foundation of the Hungarian Society of Pulmonologists (2014, TDL) and Janos Bolyai Research Scholarship of the Hungarian Academy of Sciences (AB)