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The biomineralization-inspired preparation of inorganic hybrid materials has attracted attention. Here, we report a new approach to the orientation control of zinc oxide (ZnO) thin-film crystals through the preparation of zinc hydroxide carbonate (ZHC) by the macromolecular templates of poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(vinyl alcohol) (PVA). Using 100-nm-thick PHEMA templates, ZHC thin films with the c-axis oriented parallel to the substrate were obtained, while ZHC thin films prepared by 100-nm-thick PVA templates showed perpendicular orientation. After the thermal treatment of ZHC, the crystal orientations of the ZnO thin films were maintained. The effects of the thickness and annealing time for the polymer templates on the morphologies of the ZnO thin films were examined.

Reentrant phenomena in soft matter and biosystems have attracted considerable attention because their properties are closely related to high functionality. Here, we report a combined experimental and computational study on the self-assembly and reentrant behavior of a single-component thermotropic smectic liquid crystal toward the realization of dynamically functional materials. We have designed and synthesized a mesogenic molecule consisting of an alicyclic trans,trans -bicyclohexyl mesogen and a polar cyclic carbonate group connected by a flexible tetra(oxyethylene) spacer. The molecule exhibits an unprecedented sequence of layered smectic phases, in the order: smectic A-smectic B-reentrant smectic A. Electron density profiles and large-scale molecular dynamics simulations indicate that competition between the stacking of bicyclohexyl mesogens and the conformational flexibility of tetra(oxyethylene) chains induces this unusual reentrant behavior. Ion-conductive reentrant liquid-crystalline materials have been developed, which undergo the multistep conductivity changes in response to temperature. The reentrant liquid crystals have potential as new mesogenic materials exhibiting switching functions.

A practical and green approach to the development of color-tunable luminescent composites through in situ solvent-free synthesis of carbon dots on layered inorganic compounds is reported.

Potential applications of functional liquid crystals such as biosensors strongly rely on control of the molecular orientation at interfaces. However, little knowledge regarding detailed molecular a...

Thermotropic liquid crystals having tripeptide moieties are reported. A series of peptide chains including arginine-glycine-aspartic acid (RGD), glycine-glycine-aspartic acid (GGD), and triglycine ...

The use of visible-driven photocatalysts has fascinated attention as a capable and sustainable approach for wastewater remediation. In this work, BiOBr/carbon quantum dot (CQDs)/saponite composites (CQDs/Clay@BiOBr) were fabricated via hydrothermally using two different CQDs/Clay precursors (in-situ synthesis (IS) and physical mixing (PM)). The obtained products were characterized, and the photocatalytic performances of the prepared samples were evaluated in the photocatalytic decomposition of emerging ciprofloxacin (CIP) pharmaceutical waste. The highest CIP mineralization performance was achieved when a combination of BiOBr and CQDs/Clay (IS) with the appropriate proportion because the strong adhesion between CQDs and clay generate a great heterojunction in the composite. The stronger interaction of CQDs and better distribution of CQDs on the surface of clay in the CQDs/Clay (IS) enhanced the interaction of BiOBr and CQDs, and avoided the re-agglomeration of excess of CQDs on surface of BiOBr which reduce the active surface to receive the light and react with CIP. The ultrafast degradation rate of the optimized CQDs/Clay@BiOBr composite was better compared to others. The significant improvement in the CIP degradation efficiency of the CQDs/Clay@BiOBr composite was attributed to the excellent separation and transportation of photogenerated electrons and holes, as confirmed by photoluminescence, photocurrent density, and electrochemical impedance spectroscopy results. Moreover, the photocatalytic degradation mechanism of CIP in the CQDs/Clay@BiOBr composite was proposed based on the electronic states of each material in the composite and on a scavenger test. Thus, the proposed CQDs/Clay@BiOBr composite can be employed as a potential visible-light-driven photocatalyst for the decomposition of organic contaminants in wastewater.

The Weather Research and Forecasting (WRF) Model and the Nonhydrostatic Icosahedral Atmospheric Model (NICAM) are forced with the Global Forecast System (GFS) data and run over the United Arab Emirates (UAE) for two 4-day periods: one in the cold season (16–18 December 2017) and another in the warm season (13–15 April 2018). The models’ performance is evaluated against four observational datasets: weather station observations, eddy-covariance flux measurements at Al Ain, microwave radiometer–derived temperature profile, and twice-daily radiosonde measurements at Abu Dhabi. An overestimation of the daily mean air temperature by 1°–3°C is noticed for both models and periods. This warm bias is attributed to the reduced cloud cover and resulting increased surface downward shortwave radiation flux. A comparison with the eddy-covariance data suggested that both models also underestimate the observed albedo. However, when the models predict heavier amounts of precipitation, they tend to be colder than observations, typically by 2°–3°C. NICAM and WRF overpredict the strength of the near-surface wind speed at all weather stations by roughly 1–3 m s−1, which has been attributed to a poor representation of its subgrid-scale fluctuations and surface drag parameterization. WRF tends to be wetter and NICAM drier than the station observations, possibly because of differences in the cloud microphysics schemes. While the performance of both models for the near-surface fields is comparable, NICAM outperforms WRF in the simulation of vertical profiles of temperature, relative humidity, and wind speed, being able to partially correct some of the biases in the GFS data.

We here report a new approach to develop self-healing shape memory supramolecular liquid-crystalline (LC) networks through self-assembly of molecular building blocks via combination of hydrogen bonding and coordination bonding. We have designed and synthesized supramolecular LC polymers and networks based on the complexation of a forklike mesogenic ligand with Ag+ ions and carboxylic acids. Unidirectionally aligned fibers and free-standing films forming layered LC nanostructures have been obtained for the supramolecular LC networks. We have found that hybrid supramolecular LC networks formed through metal–ligand interactions and hydrogen bonding exhibit both self-healing properties and shape memory functions, while hydrogen-bonded LC networks only show self-healing properties. The combination of hydrogen bonds and metal–ligand interactions allows the tuning of intermolecular interactions and self-assembled structures, leading to the formation of the dynamic supramolecular LC materials. The new material design presented here has potential for the development of smart LC materials and functional LC membranes with tunable responsiveness., New supramolecular hybrid liquid-crystalline networks exhibiting self-healing and shape memory properties are developed by self-assembly of small components through hydrogen bonding interactions and coordination bonding.

The 3rd model intercomparison project (MIP) of atmospheric dispersion model targeting on 137Cs emitted from the Fukushima Daiichi Nuclear Power Plant (FDNPP) in March 2011 was conducted (Sato et al. 2020). Nine models participated in the 3rd MIP. All participated models used the identical source term of Katata et al. (2015) and the identical meteorological data (Sekiyama and Kajino, 2020) as in the previous MIP (i.e., 2nd MIP Sato et al. 2018), but finer horizontal grid resolution (1 km) than that of 2nd MIP (3 km) was used for understanding the behavior of atmospheric 137Cs measured in the vicinity of FDNPP. Results of the models elucidated that, as in the 2nd MIP, most of the observed high atmospheric 137Cs concentrations (plumes) were reasonably well simulated by the models, and the good performance of some models cancelled a bad performance of some models when used as an ensemble, which highlights the advantage of the multimodel ensemble. The analyses also indicated that the use of the finer grid resolution (1 km) improved the meteorological field in the vicinity of FNDPP. As a consequence, the atmospheric 137Cs measured near FDNPP was more reasonably reproduced in 3rd MIP than 2nd MIP.As well as the evaluation of the performance of the model, we examined the usefulness of the results of atmospheric dispersion simulation in an emergency base on the results of 2nd and 3rd MIPs. For the analyses we defined the worst situation as that plume is observed but the model does not simulate it. The analyses reported that the worst situation happened in only 3% of the total calculation period by using the multimodel ensemble, even if the absolute value of the simulated 137Cs in each model was different in the range of factor 3-6. The analyses also indicated that from six to eight models are required for making most of the advantages of the multimodel ensemble.

The third model intercomparison project (MIP) for investigating the atmospheric behavior of atmospheric caesium-137 (137Cs) emitted from Fukushima Daiichi Nuclear Power Plant (FDNPP) (3rd FDNPP-MIP), Japan, in March 2011, was conducted. A finer horizontal grid spacing (1 km) was used than in the previous FDNPP-MIP (2nd FDNPP-MIP, Sato et al., 2018; 3 km) to evaluate the models’ performance for high-concentration events measured near FDNPP. Nine of the models used in the 2nd FDNPP-MIP were also used in the 3rd FDNPP-MIP, and all models used identical source terms and meteorological fields. The performance of the models was evaluated through a comparison with observational data. Our analyses indicated that most of the observed high atmospheric 137Cs concentrations (plumes) were reasonably well simulated by the models, and the good performance of some models improved the performance of the multimodel, highlighting the advantage of using a multimodel ensemble. The analyses also confirmed that the use of a finer grid resolution resulted in the meteorological field near FDNPP being better reproduced in the 3rd FDNPP-MIP, and the performance of the models was better than that of the 2nd FDNPP MIP. The good representation of the wind field resulted in the reasonable simulation of the narrow distribution of high deposition amount to the northwest of FDNPP and the reduction of the overestimation in deposition amount over the area to the south of FDNPP compared to the 2nd FDNPP MIP. In contrast, the performance of the models in simulating plumes observed over the Nakadori area, the northern part of Gunma, and the Tokyo Metropolitan Area (TMA) was slightly worse than in the 2nd FDNPP-MIP.

Following the previous atmospheric transport model intercomparison project (MIP2: Sato et al, 2018), a new project of model intercomparison (MIP3) has been conducted in which, out of 12 models in MIP2, 9 models are participating. The main aim of MIP3 is to examine the effects of using a refined meteorological data with a finer horizontal resolution of 1 km (Sekiyama et al., 2019). This paper describes outline of the preliminary results of MIP3. The horizontal distribution Cs-137 deposition in the eastern part of Honshu Island (the main island of Japan) calculated by the models were compared with the aerial survey results to find that the simple ensemble average of the 9 models was a little worse than that of the 12-model ensemble in MIP2 in terms of the statistical index RANK, which is the combination of the correlation coefficient, the fractional bias, the figure of merit in space and KPS. This slightly poorer performance is tentatively considered to be caused partially by the absence of three models which showed rather broad deposition patterns and by the underestimation in the Nakadori area (the middle part of Fukushima Pref.). However, in the sector in the northwestern direction from the accidental site which had the largest deposition, the deposition pattern simulated by the MIP3 ensemble, if compared with that of MIP2, is more consistent with the survey result. As for the atmospheric concentrations, although the model performance for the plumes that traveled over wider areas was found to be slightly poorer for MIP3 than MIP2, it was found that the MIP3 ensemble generally showed better performance for the plumes that affected the near area in the Hamadori area (the coastal part of Fukushima Pref.). The better performance of the MIP3 in this area can be attributed to the better representation of topography in the meteorological simulation.

The Fukushima Dai-ichi Nuclear Power Plant accidents following the March 11, 2011 Tohoku earthquake, and subsequent tsunami released radioactive materials into the atmosphere and caused significant public health concerns, particularly thyroid cancers in children. However, the lack of measurement data for atmospheric concentrations of

Novel liquid-crystalline N,N′-diarylsquaramides 1a and 1b were designed and synthesized, and their properties were elucidated. The squaramides exhibited thermotropic columnar liquid-crystalline phases at low temperature including room temperature. X-ray crystallographic analysis of methoxy derivative 1c showed the self-assembly of face-to-faced dimer through π-π interaction.

Seit der Entdeckung des flussigkristallinen Zustandes im Jahr 1888 wurden Flussigkristalle unter Einsatz verschiedener Technologien in unterschiedlichen Disziplinen eingehend erforscht. In letzter Zeit wurden dank der Fortschritte bei Synthese- und Charakterisierungsmethoden ein neuartiges Molekuldesign und neue selbstorganisierte Strukturen entwickelt. Fur diese Flussigkristalle, deren neuartige Funktionen und Eigenschaften sich von ihren Nanostrukturen und ihrer Ausrichtung ableiten, wurde eine Vielzahl moglicher Anwendungen vorgeschlagen, etwa im Energietransport, in Trennverfahren fur die Umwelttechnik, als Sensoren, Aktuatoren oder Template sowie auf der Grundlage von Farbanderungen oder elektrooptischen Effekten. Dieser Aufsatz prasentiert die neuesten Fortschritte bei Flussigkristallen, die zu einer neuen Generation von Materialien fuhren konnten.

形態: カラー図版あり, Physical characteristics: Original contains color illustrations, 資料番号: PA1810045000

Supramolecular self-assembly of 24 forklike mesogenic ligands and 12 transition metal ions leads to formation of giant spherical coordination complexes that exhibit liquid-crystalline (LC) phases. Self-healing LC supramolecular gels have also been obtained by introduction of these LC nanostructured supramolecular giant spherical complexes into dynamic covalent networks formed by cross-linkers and bifunctional polymers. The giant spherical structures of the Pd(II) complexes with 72 rodlike moieties on the periphery have been characterized by NMR, diffusion-ordered NMR spectroscopy, and mass spectrometry. These complexes are stable and exhibit lyotropic LC behavior, while the mesogenic ligands show thermotropic LC properties. The self-assembled LC structures of the spherical complexes can be tuned by the length of the rodlike moieties.

The design and functions of liquid-crystalline (LC) polymers with classifying them into conventional-, supramolecular-, dendritic- and network-type LC polymers are described. LC polymers show new functions as new devices in the field of energy and environment by incorporating mesogenic moieties exhibiting photonic, electronic and ionic functions. Supramolecular LC polymers show dynamic and unique properties because the mesogenic moieties are built with non-covalent interactions. Dendritic-type LC polymers exhibit liquid crystallinity by nanosegregation of aromatic and aliphatic moieties. Dendritic fork-like mesogens have also been prepared. A variety of nonmesogeic functional building blocks including fullerene, π-conjugated moieties, catenane, rotaxane and others can be incorporated into LC phases by attaching these dendritic moieties. LC networks are constructed in situ polymerization of polymerizable nematic or nanostructured liquid crystals. The specific characteristics of the LC networks have generated new research trends to develop well-defined polymers that exhibit optical, transport and separation properties. In these materials, through suitable design of LC monomers, the preservation of smectic, columnar and bicontinuous cubic phases has been successfully used for the development of membranes with one-dimensional, two-dimensional and three-dimensional nanostructures. The design and functions of various liquid-crystalline (LC) polymers including main-chain, side-chain and network LC polymers as well as dendritic structures are described. These polymeric LC materials can be applied for electro-, ion-, photo-active materials as well as mechanically tough materials. The introduction of supramolecular design has also generated a new category of functional LC materials.

Dendritic molecules having several rigid-rod moieties can be applied to induce liquid crystallinity for a variety of non-mesomorphic functional molecules such as metal complexes, nanoparticles, fullerenes and π-conjugated molecules when these dendritic molecules are covalently bonded to those non-mesomorphic molecules. These complex molecules are called supermolecular liquid crystals. Due to the cooperation of several mesogenic moieties, these dendritic molecules exhibit very stable liquid-crystalline (LC) phases. We have used fork-shaped LC dendrons having two or three rigid-rod moieties to induce liquid crystallinity for functional molecules such as interlocked molecules and π-conjugated molecules. In these fork-like molecules, the rigid-rod cores are attached to the 3,4,5-position of the phenyl moieties through flexible spacer, and these molecules are bonded to functional molecules through the 1-position. They basically form smectic LC phases, which induce the layered arrangement of functional moieties. Here we report on a new family of fork-like mesogens containing a hydrogen bonding moiety or an ionic group. They are designed to build supramolecular materials.

International audience; A model intercomparison of the atmospheric dispersion of cesium-137 (137Cs) emitted after the Fukushima Daiichi Nuclear Power Plant accident in Japan was conducted to understand the behavior of atmospheric 137Cs in greater detail. The same meteorological data with a fine spatiotemporal resolution and an emission inventory were applied to all models to exclude the differences among the models originating from differences in meteorological and emission data. The meteorological data were used for initial, boundary, and nudging data or offline meteorological field. Furthermore, a horizontal grid with the same resolution as that of the meteorological data was adopted for all models. This setup enabled us to focus on model variability originating from the processes included in each model, for example, physical processes. The multimodel ensemble captured 40% of the atmospheric 137Cs events observed by measurements, and the figure of merit in space for the total deposition of 137Cs exceeded 80. The lower score of the atmospheric 137Cs than that of the deposition originated from the difference in timing between observed and simulated atmospheric 137Cs. Our analyses indicated that meteorological data were most critical for reproducing the atmospheric 137Cs events. The results further revealed that differences in 137Cs concentrations among the models originated from deposition and diffusion processes when the meteorological field was simulated reasonably well. The models with small deposition fluxes produced higher scores for atmospheric 137Cs, and those with strong diffusion succeeded in capturing the high 137Cs concentrations observed; however, they also tended to overestimate the concentrations. ©2018. The Authors.

A nonhydrostatic stretched-grid (SG) model is used to analyze the large-scale errors generated by stretching horizontal grids and their influence on a region of interest. Simulations by a fully compressible, nonhydrostatic global atmospheric model, the Nonhydrostatic Icosahedral Atmospheric Model (NICAM), and its SG regional model, stretched-NICAM, were performed for the months of March, April, and May of 2011 using various resolutions and stretching factors. A comparison of week-long accumulative precipitation amounts between the Tropical Rainfall Measuring Mission (TRMM) satellite data and the quasi-uniform and SG simulations showed that a stretched run better represents storms and associated precipitation because the errors generated in the outer regions with coarser grid spacing do not significantly affect the inner domain centered at the focal point. For season-long simulations, in one particular set of stretched runs with the focal point located in the eastern United States, the artificial suppression of baroclinic development of midlatitude eddies in the Southern Hemisphere weakened the eddy-driven polar-front jet (PFJ), which yielded a cold bias at mid- to high latitudes. However, in the Northern Hemisphere, in contrast, the aforementioned changes are less apparent. Therefore, for the SG runs, the mean temperature was maintained at the region of interest, and an increased amount of moderate to heavy precipitation, which is also frequently found in the TRMM data, was observed; thus, the benefits of increased resolution were realized. However, careful attention must be given when applying the SG model because a regional climate response to the change in the large-scale circulations may not be fully accounted for.

The Fukushima Dai-ichi Nuclear Power Plant accidents following the March 11, 2011 Tohoku earthquake, and subsequent tsunami released radioactive materials into the atmosphere and caused significant public health concerns, particularly thyroid cancers in children. However, the lack of measurement data for atmospheric concentrations of 131I has caused persistent and widespread uncertainty. This study estimated the maximum potential thyroid doses of inhaled 131I in the early post-accident phase between March 12 and 23, 2011 by using the hourly measured data of the 137Cs concentrations at 101 suspended particulate matter (SPM) monitoring sites, a new multi-model ensemble (MME) method of simulating 137Cs concentrations using two Atmospheric Transport and Deposition Models (ATDMs), the 131I/137Cs ratio obtained from measurement data analysis, and the internal exposure model. Based on the measurements, the maximum potential thyroid doses were estimated at 3.1–160 mSv at 5 sites in the Fukushima-Hamadori area for 1-year-old children assumed to remain outdoors, whereas they were less than 4.3 mSv at the other sites in the base case of the 131I/137Cs ratio. The spatial distribution of the maximum potential of early inhalation doses was estimated by using the MME and measurements. The inhalation thyroid doses in the evacuation scenarios were compared to the estimates reported by previous studies. The results of the present study were almost congruent with the outcomes of previous investigations except for thyroid doses contributed by highly contaminated plumes on March 12 and 15. The sensitivity analysis for the 131I/137Cs ratio indicated that these plumes carried the potential to significantly increase the thyroid doses of residents.

We have developed a seamless global-to-regional model to calculate atmospheric aerosol chemistry by coupling existing aerosol and chemical modules to a global cloud-system-resolving model (NICAM-Chem). The model can simulate air pollutants with various grid sizes ranging from global low resolution (~200 km) on yearly scales to regional high resolution (~10 km) on monthly scales and global high resolution (

Since the discovery of the liquid-crystalline state in 1888, liquid crystal science has made great advances through fusion with various technologies and disciplines. Recently, new molecular design strategies and new self-assembled structures have been developed as a result of the progress made in synthetic procedures and characterization techniques. Since these liquid crystals exhibit new functions and properties derived from their nanostructures and alignment, a variety of new functions for liquid crystals, such as transport for energy applications, separation for environmental applications, chromism, sensing, electrooptical effects, actuation, and templating have been proposed. This Review presents recent advances of liquid crystals that should contribute to the next generation of materials.

An aerosol-coupled global nonhydrostatic model with a stretched-grid system has been developed. Circulations over the global and target domains are simulated with a single model, which includes fine meshes covering the target region to calculate meso-scale circulations. The stretched global model involves lower computational costs to simulate atmospheric aerosols with fine horizontal resolutions compared with a global uniform nonhydrostatic model, whereas it may require higher computational costs compared with the general regional models, because the stretched-grid system calculates inside and outside the target domain. As opposed to general regional models, the stretched-grid system requires neither a nesting technique nor lateral boundary conditions. In this study, we developed a new-type regional model for the simulation of aerosols over Japan, especially in the Kanto areas surrounding Tokyo, with a maximum horizontal resolution of approximately 10 km. This model usually reproduces temporal variations and their averages of the observed weather around Japan. This model generally reproduces monthly mean distributions of the observed sulfate and SO2 over East Asia, with high correlations (R > 0.6), but the underestimation of the simulated concentrations by 40% (sulfate) and 50% (SO2). Their underestimation of the simulated sulfate and SO2 concentrations over East Asia are strongly affected by their underestimation in China and possibly by the uncertainty of the simulated precipitation around Japan. In the Kanto area, this model succeeds in simulating the wind patterns and the diurnal transitions around the center of the Kanto area, although it is inadequate to simulate the wind patterns and the diurnal transitions at some sites located at the edge of the Kanto area and surrounded on three sides by mountains, e.g., Maebashi, mainly due to the insufficient horizontal resolution. This model also generally reproduces both diurnal and synoptic variations of the observed and/or a regional aerosol-transport model, WRF-CMAQ, simulated EC, sulfate, and SO2 concentrations in the Kanto area, especially with their high correlation (R > 0.5) at Komae/Tokyo. Although the aerosol module used in this study is relatively simplified compared to the general regional aerosol models, this study reveals that our proposed model with the stretched-grid system can be applicable for the regional aerosol simulation.

Lactococcus lactis subsp. lactis has been isolated from the intestines of marine fish and is a candidate probiotic for aquaculture. In order to use the bacterium as a probiotic, properties such as bile tolerance need to be assessed. Here, we compared bile tolerance in L. lactis strains derived from different sources. Three L. lactis subsp. lactis strains from marine fish (MFL), freshwater fish (FFL), and cheese starter (CSL) were used along with an Lactococcus lactis subsp. cremoris strain from cheese starter (CSC). The four strains were grown under various culture conditions: deMan-Rogosa-Sharpe (MRS) broth containing bile salts/acids, MRS agar containing oxgall, and phosphate-buffered saline (PBS) containing fish bile. Survival/growth of the strains in the presence of sodium cholate and sodium deoxycholate varied in the order MFL, CSL > CSC > FFL; in the presence of sodium taurocholate, the order was MFL > CSL > CSC > FFL. In liquid media containing various concentrations of oxgall, survival of the strains was observed in the order MFL > CSL > FFL and CSC. The survival of MFL was not affected by bile collected from the goldfish (Carassius auratus subsp. auratus) or the puffer fish (Takifugu niphobles), although the other strains showed significant inhibition of growth. It is a novel and beneficial finding that MFL has the highest resistance to bile acid.

Lactic acid bacteria (LAB) were isolated from the intestinal tract of the wild clam Meretrix lamarckii caught from the coastal waters of Kashima, Ibaraki, Japan. As many as 415 isolates were obtained using the culture method, of which 70 were considered presumptive LAB strains based on phenotypic tests. Phylogenetic analysis of these presumptive isolates of LAB based on the sequence of the 16S rRNA gene demonstrated that the species belonged to several genera of Lactobacillus, Lactococcus and Pediococcus. Interestingly, however, the species composition was different between the samples in July and October 2010. Further analyses based on the fermentation profiles revealed that the LAB from the clam caught in July 2010 were identified to be Lactobacillus curvatus, Lactobacillus plantarum, Lactococcus lactis subsp. cremoris and Pediococcus pentosaceus, whereas those in October 2010 were identified to be Lactobacillus plantarum, Lactococcus lactis subsp. lactis and P. pentosaceus. The diversity of LAB in the intestinal tract of the clam suggests that the filter feeder bivalves such as M. lamarckii are a rich repository of marine isolates of LAB.

A novel thin-layer electrolysis flow cell based on the ion transfer at the liquid|liquid interface was proposed for the absolute determination of a sub-nanomole ionic species. By using the conducting polymer-coated electrode as an electrode in organic phase, the flow cell was developed as a laminate structure with a thin aqueous layer and a thin organic layer, which were set between an Ag/AgCl electrode and the conducting polymer-coated electrode. Its simple structure made it possible to miniaturize the flow cell, and the required sample volume was reduced to only 1 μl. In the present electrolysis cell, both quantitative extraction and quantitative back-extraction of total amount of the ionic species were achieved. This advantage was applied to two methods for absolute determination. One is that by flow injection method, and the other is that by pre-concentration into the thin organic phase followed by back-extraction of the species from the thin Org to the thin aqueous phase (i.e., the stripping technique). In these methods, coulometrical determination of sub-nanomol ionic species was realized without a calibration curve.

This article reviews the development of a thin-layer electrolysis cell with both a thin aqueous phase and a thin organic phase for ion transfer at the liquid|liquid interface for the absolute determination of a redox-inactive ion. In particular, an improvement of the cell performance by using a conducting polymer-coated electrode in the organic phase is discussed. The applicability of the thin-layer electrolysis cell to the absolute determination of redox-inactive ions using the flow-injection method or stripping method is also described.

[1] In marine stratocumulus-capped boundary layers under strong inversions, the timescale for thermodynamic adjustment is roughly a day, much shorter than the multiday timescale for inversion height adjustment. Slow-manifold analysis is introduced to exploit this timescale separation when boundary layer air columns experience only slow changes in their boundary conditions. Its essence is that the thermodynamic structure of the boundary layer remains approximately slaved to its inversion height and the instantaneous boundary conditions; this slaved structure determines the entrainment rate and hence the slow evolution of the inversion height and can be regarded as a one-dimensional slow manifold. Slow-manifold analysis is applied to mixed-layer model and large-eddy simulations of an idealized nocturnal stratocumulus-capped boundary layer. Both models are found to have multiple equilibria; depending on the initial inversion height, the simulations slowly evolve toward a shallow thin-cloud boundary layer or a deep, well-mixed thick cloud boundary layer. In the mixed-layer model, this can be described using a single slow manifold bifurcated by an unstable equilibrium inversion height which separates a branch that evolves toward a deep steady state from a branch which shallows indefinitely. In the large-eddy simulations, there are two separate slow manifolds (one of which becomes unstable if cloud droplet concentration is reduced). On one, the boundary layer is well-mixed and deepens to a thick-cloud steady state. On the other, the boundary layer is decoupled and shallows to a thin-cloud steady state. If the initial inversion height supports an optically thick but nearly nondrizzling cloud, it evolves onto the well-mixed manifold; if the initial cloud layer is either too thin to efficiently radiatively cool, or thick enough to heavily drizzle, it evolves onto the decoupled manifold. Applications to analysis of stratocumulus observations and to pockets of open cells and ship tracks are proposed.

The sensitivity of a stratocumulus-capped mixed layer to a change in cloud droplet concentration is evaluated with a large-eddy simulation (LES) and a mixed layer model (MLM), to see if the two model types agree on the strength of the second aerosol indirect effect. Good agreement can be obtained if the MLM entrainment closure explicitly reduces entrainment efficiency proportional to the rate of cloud droplet sedimentation at cloud top for cases in which the LES-simulated boundary layer remains well mixed, with a single peak in the vertical profile of vertical velocity variance. To achieve this agreement, the MLM entrainment closure and the drizzle parameterization must be modified from their observationally-based defaults. This is because the LES advection scheme and microphysical parameterization significantly bias the entrainment rate and precipitation profile compared to observational best guesses. Before this modification, the MLM simulates more liquid water path and much more drizzle at a given droplet concentration than the LES and is more sensitive to droplet concentration, even undergoing a drizzle-induced boundary layer collapse at low droplet concentrations. After this modification, both models predict a similar decrease of cloud liquid water path as droplet concentration increases, cancelling 30–50% of the Twomey effect for our case. The agreement breaks down at the lowest simulated droplet concentrations, for which the boundary layer in the LES is not well mixed. Our results highlight issues with both types of model. Potential LES biases due to inadequate resolution, subgrid mixing and microphysics must be carefully considered when trying to make a quantitative inference of the second indirect effect from an LES of a stratocumulus-topped boundary layer. On the other hand, even slight internal decoupling of the boundary layer invalidates MLM-predicted sensitivity to droplet concentrations.

Received 12 February 2007; revised 11 July 2007; accepted 2 August 2007; published 27 December 2007. [1] This study presents an intercomparison of single-column model simulations of a nocturnal heavily drizzling marine stratocumulus-topped boundary layer. Initial conditions and forcings are based on nocturnal flight observations off the coast of California during the DYCOMS-II field experiment. Differences in turbulent and microphysical parameterizations between models were isolated by slightly idealizing and standardizing the specification of surface and radiative fluxes. For most participating models, the case was run at both typical operational vertical resolution of about 100 m and also at high vertical resolution of about 10 m. As in prior stratocumulus intercomparisons, the simulations quickly develop considerable scatter in liquid water path (LWP) between models. However, the simulated dependence of cloud base drizzle fluxes on LWP in most models is broadly consistent with recent observations. Sensitivity tests with drizzle turned off show that drizzle substantially decreases LWP for many models. The sensitivity of entrainment rate to drizzle is more muted. Simulated LWP and entrainment are also sensitive to the inclusion of cloud droplet sedimentation. Many models underestimate the fraction of drizzle that evaporates below cloud base, which may distort the simulated feedbacks of drizzle on turbulence, entrainment, and LWP.

[1] The effect of cloud droplet sedimentation on the entrainment rate and liquid water path of a nocturnal nondrizzling stratocumulus layer is examined using large-eddy simulations (LES) with bulk microphysics. In agreement with a prior study by Ackerman et al. (2004), sedimentation is found to decrease entrainment rate and thereby increase liquid water path. They suggested this is due to reduction of boundary-layer turbulence. Our simulations suggest otherwise. Instead, sedimentation reduces entrainment by removing liquid water from the entrainment zone. This inhibits two mechanisms that promote the sinking of entrained air into the cloud layer–entrainment-induced evaporative cooling and longwave radiative cooling. A sensitivity study shows that the radiative effect is less important than the reduced evaporation. A possible parameterization of the effect of sedimentation on entrainment rate in a mixed layer model is proposed and tested. Since the droplet sedimentation rate is inversely related to cloud droplet (and presumably aerosol) concentration and nearly nondrizzling marine stratocumulus are widespread, sedimentation impacts on stratocumulus entrainment efficiency should be considered in climate model simulations of the aerosol indirect effect.

In this study, a new method is proposed for the depiction of the atmospheric transportation of the 137Cs emitted from the Fukushima Daiichi Nuclear Power Station accident. This method employs a combination of the results of two aerosol model ensembles and the hourly observed atmospheric 137Cs concentration at surface level during 14–23 March 2011 at 90 sites in the suspended particulate matter monitoring network. The new method elucidates accurate transport routes and the distribution of the surface-level atmospheric 137Cs relevant to eight plume events that were previously identified. The model ensemble simulates the main features of the observed distribution of surface-level atmospheric 137Cs. However, significant differences were found in some cases, and this suggests the need to improve the modeling of the emission scenario, plume height, wet deposition process, and plume propagation in the Abukuma Mountain region. The contributions of these error sources differ in the early and dissipating phases of each event, depending on the meteorological conditions.