Direct Oxidation of Methane to Methanol over Transition-Metal-Free Ferrierite Zeolite Catalysts.

Direct oxidation of methane to methanol was reported to be highly dependent on the transition- or noble-metal-loading catalysts in the past decades. Here, we show that the transition-metal-free aluminosilicate ferrierite (FER) zeolite effectively catalyzed methane and N2O to methanol for the first time. The distorted tetracoordinated Al in the framework and pentacoordinated Al on the extra framework formed during calcination, activation, and reaction processes were confirmed as the potential active centers. The possible reaction pathway similar to the Fe-containing zeolites was advocated based on the reaction results using different oxidants, N2O adsorption FTIR spectra, and 27Al MAS NMR spectra. The stable and efficient methanol production capacity of FER zeolite was ascribed to the two-dimensional straight channels and its distinctive Al distribution of FER zeolite (CP914C) from Zeolyst. The transition-metal-free FER zeolite performed better than the record in the literature and our recent results using transition-metal-containing catalysts in terms of selectivity and formation rate of methanol and stability. This work has great significance and prospects for utilizing CH4 and N2O as resources and will open new avenues for methane oxidation.

Understanding the effect of spatially separated Cu and acid sites in zeolite catalysts on oxidation of methane.

Unraveling the effect of spatially separated bifunctional sites on catalytic reactions is significant yet challenging. In this report, we investigate the role of spatial separation on the oxidation of methane in a series of Cu-exchanged aluminosilicate zeolites. Regulation of the bifunctional sites is done either through studying a physical mixture of Cu-exchanged zeolites and acidic zeolites or by systematically varying the Cu and acid density within a family of zeolite materials. We show that separated Cu and acid sites are beneficial for the formation of hydrocarbons while high-density Cu sites, which are closer together, facilitate the production of CO2. By contrast, a balance of the spatial separation of Cu and acid sites shows more favorable formation of methanol. This work will further guide approaches to methane oxidation to methanol and open an avenue for promoting hydrocarbon synthesis using methanol as an intermediate.

Accelerated Fear Extinction by Regular Light-Intensity Exercise: A Possible Role of Hippocampal BDNF-TrkB Signaling.

PURPOSE: Growing concern exists worldwide about stress-related mental disorders, such as posttraumatic stress disorder (PTSD), often linked to hippocampal dysfunctions. Recognizing this connection, regular light-intensity exercise (LIE)-such as yoga, walking, or slow jogging-may offer a solution. Easily accessible even to vulnerable individuals, LIE has been found to enhance hippocampus-based cognitive functions through the stimulation of neurotrophic factors like brain-derived neurotrophic factor (BDNF). A prior study that demonstrated BDNF's role in extinguishing original fear memory further leads us to propose that a consistent LIE training might drive fear extinction learning, offering potential therapeutic benefits through BDNF signaling. METHODS: Eleven-week-old Wistar rats underwent 4 wk of training under conditions of sedentary, LIE, or moderate-intensity exercise (MOE) after contextual or auditory fear conditioning. Subsequently, fear extinction tests were performed. We then administered intraperitoneal (i.p.) ANA-12, a selective antagonist of tropomyosin receptor kinase B (TrkB), or a vehicle to explore the role of BDNF signaling in exercise-induced fear extinction among the LIE rats. Following the regular exercise training, further fear extinction tests were conducted, and hippocampal protein analysis was performed using Western blotting. RESULTS: Both LIE and MOE over 4 wk accelerated hippocampus-associated contextual fear extinction compared with sedentary. In addition, 4 wk of LIE with i.p. administered vehicle increased hippocampal BDNF and TrkB protein levels. In contrast, i.p. ANA-12 administration fully blocked the LIE-enhanced protein levels and its effect on contextual fear extinction. CONCLUSIONS: Our findings reveal that LIE regimen promotes fear extinction learning, at least partially tied to hippocampal BDNF-TrkB signaling. This suggests that even regular light exercise could alleviate the excessive fear response in anxiety disorders and PTSD, providing hope for those affected.

Influence of non-uniform flow on toxic elements transport in soil column percolation test.

The influence of flow channels on the leaching behavior of toxic elements in contaminated soil cannot be neglected in a column percolation test. This study presents a visualization of the flow channel formed in the soil and evaluated the relationship between the leaching behavior of soil components and flow. We conducted column percolation tests with two types of filling methods (Compaction and No compaction) and used X-ray computed tomography to visualize the soil structure and non-uniform flow. Additionally, the variations of flow in a cross section of water were evaluated using hydraulic conductivity based on differential pressure. Under No compaction, a flow occurred throughout the soil column at the beginning of the water passage, but a non-uniform flow emerged as the liquid-solid ratio increased; under Compaction, a non-uniform flow was formed from the beginning of water passage. The leaching behavior of the major components and toxic elements from soil with high adsorptive properties was significantly affected by the filling method up to a liquid-solid ratio of 2. These results suggest that the non-uniform flow formed in the column percolation test has a significant impact on the leaching of soil components.

Potentially toxic elements pose significant and long-term human health risks in river basin districts with abandoned gold mines.

Gold (Au) mining area is known to be one of the major sources of toxic elements; however, the potential risks of toxic elements from abandoned Au mines to the surrounding river basin districts and human exposure pathways to toxic elements need to be clarified. In this study, the distribution and mobilities of nine toxic elements (As, Cd, Cu, Pb, Sb, Zn, Cr, Ni and V) in Kesennuma City, Tohoku Region in Japan, a typical Au-mining district with several river basins, were studied through a geochemical survey (including element total concentrations and water-/acid-leaching concentrations determinations, as well as GB calculations), and environmental assessment on these elements in soil, river sediment, and river water samples from the study area. The contamination evaluation by index of geo-accumulation (Igeo) and enrichment factor (EF) suggested that As, Cu, Ni and Sb enrichments were greatly observed in the vicinity of the abandoned Au mines; moreover, calculated GB upper values for Cu in the river sediment surpass that of Tohoku Region. It has been found in this study that each element has particular mobility, which eventually influences its exposure pathway to humans. For instance, As in soil and sediment poses adverse non-carcinogenic risks and unacceptable carcinogenic risks to especially children mainly through groundwater ingestion. To minimize the potential risks associated with exposure to toxic elements in Au-mining districts, effective risk management measures should be implemented around river system by Au-mining companies even after their long-time closures, based on the consideration of each element's mobility.

Role of water in unexpectedly large changes in emission flux of volatile organic compounds in soils under dynamic temperature conditions.

Understanding the diffusive transport behavior of volatile organic compounds (VOCs) in near-surface soils is important because soil VOC emissions affect atmospheric conditions and climate. Previous studies have suggested that temperature changes affect the transport behavior; however, the effect of these changes are poorly understood. Indeed, under dynamic temperature conditions, the change in VOC flux is much larger than that expected from the temperature dependency of the diffusion coefficient of VOCs in air. However, the mechanism is not well understood, although water in soil has been considered to play an important role. Here, we present the results of experiments for the upward vertical vapor-phase diffusive transport of two VOCs (benzene and tetrachloroethylene) in sandy soil under sinusoidal temperature variations of 20-30 °C, as well as its numerical representation. The results clarify that the unexpectedly large changes in emission flux can occur as a result of changes in the VOC concentration gradient due to VOC release (volatilization) from/trapping (dissolution) into water, and that such flux changes may occur in various environments. This study suggests the importance of a global evaluation of soil VOC emissions by continuous measurements in various soil environments and/or predictions through numerical simulations with thorough consideration of the role of water in dynamic soil environments.

Novel chemical stimulation for geothermal reservoirs by chelating agent driven selective mineral dissolution in fractured rocks.

Improving geothermal systems through hydraulic stimulation to create highly permeable fractured rocks can induce seismicity. Therefore, the technique must be applied at a moderate intensity; this has led to concerns of insufficient permeability enhancement. Adding chemical stimulation can mitigate these issues, but traditional methods using strong mineral acids have challenges in terms of achieving mineral dissolution over long distances and highly variable fluid chemistry. Here, we demonstrate a novel chemical stimulation method for improving the permeability of rock fractures using a chelating agent that substantially enhances the dissolution rate of specific minerals to create voids that are sustained under crustal stress without the challenges associated with the traditional methods. Applying this agent to fractured granite samples under confining stress at 200 °C in conjunction with 20 wt% aqueous solutions of sodium salts of environmentally friendly chelating agents (N-(2-hydroxyethyl)ethylenediamine-N, N', N'-triacetic acid and N, N-bis(carboxymethyl)-L-glutamic acid) at pH 4 was assessed. A significant permeability enhancement of up to approximately sixfold was observed within 2 h, primarily due to the formation of voids based on the selective dissolution of biotite. These results demonstrate a new approach for chemical stimulation.

Dynamic evaluation method for planning sustainable landfills using GIS and multi-criteria in areas of urban sprawl with land-use conflicts.

Landfill site selection is problematic in many countries, especially developing nations where there is rapid population growth, which leads to high levels of inadequate waste disposal. To find sustainable landfill sites in sprawling cities, this study presents an approach that combines geographic information system (GIS) with multi-criteria (social, environmental and, technical criteria) and the population growth projection. The greater Maputo area in Mozambique was selected as a representative city for the study, which is undergoing rapid urbanization. Six criteria, i.e., land use, transport networks, hydrology, conservation reserve, geology and slope, were considered and overlaid in the GIS using an analytic hierarchy process (AHP). The arithmetic projection of the population trend suggests that the greater Maputo area is experiencing a rapid and uncontrolled population growth, especially in Matola city. These pronounced changes in population then significantly change the landfill placement decision making. Dynamic and static scenarios were created, based on the analysis of multi-criteria and the areas likely to undergo future increased population growth. A comparative evaluation in a scenario of dynamic behavior considering future population showed that suitable areas for landfill sites have been drastically modified due to social and environmental factors affected by population distribution in some regions. The results indicate that some suitable areas can generate land use conflicts due to population growth with unplanned land use expansion. Finally, the western part of Matola city is recognized as the most recommendable landfill site, which can serve both Maputo and Matola city with affordable costs. This study provides an effective landfill placement decision making approach, which is possible to be applied anywhere, especially in developing countries to improve sustainable municipal solid waste management systems.

Enhancement of aragonite mineralization with a chelating agent for CO2 storage and utilization at low to moderate temperatures.

Among the CaCO3 polymorphs, aragonite demonstrates a better performance as a filler material in the paper and plastic industries. Despite being ideal from the environmental protection perspective, the production of aragonite particles via CO2 mineralization of rocks is hindered by the difficulty in achieving high production efficiencies and purities, which, however, can be mitigated by exploiting the potential ability of chelating agents on metal ions extraction and carbonation controlling. Herein, chelating agent N,N-dicarboxymethyl glutamic acid (GLDA) was used to enhance the extraction of Ca from calcium silicate and facilitate the production of aragonite particles during the subsequent Ca carbonation. CO2 mineralization was promoted in the presence of 0.01-0.1 M GLDA at ≤ 80 °C, with the maximal CaCO3 production efficiency reached 308 g/kg of calcium silicate in 60 min using 0.03 M GLDA, which is 15.5 times higher than that without GLDA. In addition, GLDA showed excellent effects on promoting aragonite precipitation, e.g., the content of aragonite was only 5.1% in the absence of GLDA at 50 °C, whereas highly pure (> 90%, increased by a factor of 18) and morphologically uniform aragonite was obtained using ≥ 0.05 M GLDA under identical conditions. Aragonite particle morphologies could also be controlled by varying the GLDA concentration and carbonation temperature. This study proposed a carbon-negative aragonite production method, demonstrated the possibility of enhanced and controlled aragonite particle production during the CO2 mineralization of calcium silicates in the presence of chelating agents.

Using data-driven analysis of geochemical environmental information to infer the environmental impact of closed mines.

River sediments have the effect of aggregating geochemical environmental information, such as that related to geological and artificial pollution resulting from mine closure. This information comprises high-dimensional data and is related to the distribution and quantities of elements in river sediments. However, accessing and interpreting this geochemical information can be difficult. This study employed a data-driven analysis that can be mathematically and statistically reduced in dimension. Using high-dimensional geochemical and environmental information on river sediments, this study evaluated the environmental impact of closed mines. Sample for analysis were collected from three rivers. There are differences in the existence of mines and mine wastewater treatment methods in this river. A total of 33 elements were measured in river sediments. Frequency distribution analysis and Principal component analysis revealed that the elements had unique distribution and frequency characteristics in each river catchment. Four environmental factors could be extracted from the relationship of elements due to lower dimension. PC1 was influenced by the land use in the river area. PC2 captured the geological background. PC3 captured the mixing-diluting effect that occurs in rivers. PC4 effectively captured the effects of domestic wastewater and the effects of closed mines. The effects of the closed mines could be confirmed using the PC4 score for the Okawa River and the Akagawa River. By examining the elemental relationships obtained using these mathematical methods, it is possible to infer the effect of geological features and mines on sediment physiochemistry using existing data on river sediments.

Leaching of As and Se from coal fly ash: fundamental study for coal fly ash recycling.

Coal fly ash (CFA) is a useful recycled resource for uses such as cement raw material. To manage and evaluate safety for effective utilization of CFA, the leaching concentration and amounts of toxic elements in CFA need to be determined. In this study, 38 types of CFA and aged CFA generated in Japan were used to measure the occurrence and leaching concentration range of As and Se. In addition, the leaching characteristics over the long term were examined using statistical analysis. Leaching concentrations of As and Se from CFAs were in the range of 0.001-0.163 mg/L (average: 0.025 mg/L, median: 0.014 mg/L) and 0.001-0.189 mg/L (average: 0.071 mg/L, median: 0.055 mg/L), respectively. In general, the concentrations of aged CFAs were less than those of the CFAs with a few exceptions. Leaching concentrations of As and Se in the tank leaching test changed with time, and As and Se concentrations in the dispersions increased with stirring time. In contrast, pH of the dispersion decreased with time. The relation between As or Se and CFA factors showed that As or Se and pH or Ca were highly correlated. However, in aged CFAs for long-term use, the correlation coefficient for the relation between As and other factors was low while that for Se-S was high. Considering the effective utilization of CFA as a long-term recyclable resource, the leaching processes of As and Se in CFA would change with time depending on the environmental conditions.

A public health collaboration between medical professionals and Japan's professional football league for rubella awareness.

A public health collaboration between medical professionals and Japan's professional football league for rubella awareness.

Formation of amorphous silica nanoparticles and its impact on permeability of fractured granite in superhot geothermal environments.

Superhot geothermal environments in granitic crusts of approximately 400-500 °C are a frontier of geothermal energy. In the development of such environments, there is a concern of a reduction of permeability of fractured granite due to the formation of fine particles of amorphous silica induced by the phase change from subcritical water to supercritical water or superheated steam. However, the formation of silica particles and a resultant reduction in permeability have not been demonstrated to date. Therefore, experiments were conducted on the formation of amorphous silica particles with various combinations of temperature (430-500 °C) and pressure (20-30 MPa), in which the phase change of Si-containing water from liquid to either supercritical fluid or vapor was induced. Amorphous silica nanoparticles occurred under all conditions with smaller particles for higher temperature. The permeability of fractured granite was also observed to decrease significantly within several hours during injection of the particles into rock at 450 °C and 30 MPa under a confining stress of 40 MPa, with slower permeability reduction at a smaller number of particles or in the presence of larger aperture fractures. The present study suggests that the nanoparticles are likely to form and destroy the permeability in superhot geothermal environments, against which countermeasures should be investigated.

Data-driven analysis for source apportionment and geochemical backgrounds establishment of toxic elements and REEs in the Tohoku region, Japan.

The Tohoku region of Japan is geologically diverse, with a long agriculture and mining history; however, little information about the origins and distribution mechanisms of elements in this region has been reported. This study aims to provide fundamental insights into the effects of geological features and anthropogenic activities on various elements, including toxic elements and rare-earth elements (REEs), in the Tohoku region. A geochemical database (2007, AIST) consisting of data for 53 elements in 485 river sediment samples from the region was used, and a data-driven method combining principal component analysis (PCA) was applied for analysis. GBs for numerous types of areas, including general areas (GGB), natural environments (NGB), high anthropogenic-influenced areas (AGB) and mineralised areas (MGB) were established; especially, MGB was newly proposed in this study to illuminate the role of ore deposits. Both PCA and GBs comparison results show that geological features (especially igneous rock distribution) were the most important factor affecting elemental distribution, rather than anthropogenic activities. In the PCA, the first principal component showed that REE resources were commonly associated with the distribution of granitic rocks and REE-bearing minerals. Anthropogenic contaminations from mining, urban, and anthropogenic areas played important roles as the origin of some toxic elements (e.g. Ni, Pb, Sb). Comparisons between these GBs effectively elucidated the enrichment of certain toxic elements (e.g., Hg, Sb) in ore deposit areas. This data-driven study not only clarified the origins of toxic elements, but also revealed the location of potential REE mineral resources in the Tohoku region.

Development of a predictive model for lead, cadmium and fluorine soil-water partition coefficients using sparse multiple linear regression analysis.

In this study, we applied sparse multiple linear regression (SMLR) analysis to clarify the relationships between soil properties and adsorption characteristics for a range of soils across Japan and identify easily-obtained physical and chemical soil properties that could be used to predict K and n values of cadmium, lead and fluorine. A model was first constructed that can easily predict the K and n values from nine soil parameters (pH, cation exchange capacity, specific surface area, total carbon, soil organic matter from loss on ignition and water holding capacity, the ratio of sand, silt and clay). The K and n values of cadmium, lead and fluorine of 17 soil samples were used to verify the SMLR models by the root mean square error values obtained from 512 combinations of soil parameters. The SMLR analysis indicated that fluorine adsorption to soil may be associated with organic matter, whereas cadmium or lead adsorption to soil is more likely to be influenced by soil pH, IL. We found that an accurate K value can be predicted from more than three soil parameters for most soils. Approximately 65% of the predicted values were between 33 and 300% of their measured values for the K value; 76% of the predicted values were within ±30% of their measured values for the n value. Our findings suggest that adsorption properties of lead, cadmium and fluorine to soil can be predicted from the soil physical and chemical properties using the presented models.

Extraction of heavy metals characteristics of the 2011 Tohoku tsunami deposits using multiple classification analysis.

Tsunami deposits accumulated on the Tohoku coastal area in Japan due to the impact of the Tohoku-oki earthquake. In the study reported in this paper, we applied principal component analysis (PCA) and cluster analysis (CA) to determine the concentrations of heavy metals in tsunami deposits that had been diluted with water or digested using 1 M HCl. The results suggest that the environmental risk is relatively low, evidenced by the following geometric mean concentrations: Pb, 16 mg kg(-1) and 0.003 ml L(-1); As, 1.8 mg kg(-1) and 0.004 ml L(-1); and Cd, 0.17 mg kg(-1) and 0.0001 ml L(-1). CA was performed after outliers were excluded using PCA. The analysis grouped the concentrations of heavy metals for leaching in water and acid. For the acid case, the first cluster contained Ni, Fe, Cd, Cu, Al, Cr, Zn, and Mn; while the second contained Pb, Sb, As, and Mo. For water, the first cluster contained Ni, Fe, Al, and Cr; and the second cluster contained Mo, Sb, As, Cu, Zn, Pb, and Mn. Statistical analysis revealed that the typical toxic elements, As, Pb, and Cd have steady correlations for acid leaching but are relatively sparse for water leaching. Pb and As from the tsunami deposits seemed to reveal a kind of redox elution mechanism using 1 M HCl.

Prostaglandin E2 is a negative regulator on human plasmacytoid dendritic cells.

Prostaglandin E2 (PGE2), a major lipid derived from the metabolism of arachidonic acid, is an environmentally bioactive substance produced by inflammatory processes and acts as a cAMP up-regulator that plays an important role in immune responses. It has been reported that PGE2 has the ability to inhibit the production of interleukin-12 by myeloid dendritic cells (MDCs) and macrophages, and then induce preferential T helper type 2 (Th2) cell responses. However, little is known of the function of PGE2 for plasmacytoid dendritic cells (PDCs), which may contribute to the innate and adaptive immune response to viral infection, allergy and autoimmune diseases. In the present study, we compared the biological effect of PGE2 on human PDCs and MDCs. PGE2 caused the death of PDCs but MDCs survived. Furthermore, we found that, whereas PGE2 inhibited interferon-alpha production by PDCs in response to virus or cytosine-phosphate-guanosine, it inhibited interleukin-12 production by MDCs in response to lipopolysaccharide (LPS) or poly(I:C). Although both virus-stimulated PDCs and LPS-stimulated MDCs preferentially induced the development of interferon-gamma-producing Th1 cells, pretreatment with PGE2 led both DC subsets to attenuate their Th1-inducing capacity. These findings suggest that PGE2 represents a negative regulator on not only MDCs but also PDCs.

Plasmacytoid dendritic cells regulate Th cell responses through OX40 ligand and type I IFNs.

Dendritic cells (DCs) show a functional plasticity in determining Th responses depending on their maturational stage or on maturational signals delivered to the DCs. Human plasmacytoid DCs (PDCs) can induce either Th1- or Th2-type immune responses upon exposure to viruses or IL-3, respectively. In this study we have investigated the Th-polarizing capacity of PDCs after short (24-h) or long (72-h) culture with stimuli and have assessed the expression and function of OX40 ligand (OX40L) in PDC-mediated Th polarization in addition to type I IFN-dependent responses. IL-3-treated PDCs expressed OX40L, but produced almost no IFN-alpha in response to T cell stimulation (CD40 ligand or T cell interaction), resulting in the preferential priming of Th2 cells through OX40L-dependent mechanisms. Meanwhile, PDCs were rapidly endowed by viral infection (Sendai virus) with a high potency to develop IFN-gamma-producing Th cells depending on their capacity to residually produce IFN-alpha. Although Sendai virus-stimulated PDCs simultaneously expressed OX40L in their maturational process, the Th1-inducing effect of endogenous type I IFNs may overcome and thus conceal the OX40L-dependent Th2 responses. However, during maturation in response to Sendai virus over the longer 72-h period, the expression level of OX40L was up-regulated, whereas the residual IFN-alpha-producing ability was down-regulated, and consequently, the PDCs with prolonged Sendai virus stimulation induced Th2 responses to some extent. Thus, PDCs have the distinct means to dictate an appropriate response to environmental stimuli.

Human leukocyte antigen haplotype and autoantibodies of a family with systemic lupus erythematosus.

A search for HLA haplotypes of a family of five indicated that four members had the same haplotype. Systemic lupus erythematosus (SLE) had already developed in three of these four people. SLE has now developed in the remaining person, and the result is that all the members of the family having the same haplotype will develop SLE. Regarding these four SLE patients, the types of autoantibodies and the symptoms were different in each person, so the idea that this haplotype is strongly related to the onset of SLE but minimally related to the symptoms was suggested.