High Supersaturation Conditions Research Articles

Paths From Aerosol Particles to Activation and Cloud Droplets in Shallow Cumulus Clouds: The Roles of Entrainment and Supersaturation Fluctuations

AbstractThe activation of aerosol particles and its contribution to cloud droplet size distributions in shallow cumulus clouds are investigated by analyzing the cloud field simulation results using a Lagrangian cloud model coupled with large eddy simulation, which allows explicit simulations of the activation and tracking of each super‐droplet. Analysis is focused on the differences in activations for aerosol particles following central updraft from a cloud base (CB) and particles entrained above the cloud base (EA). Time series of various variables following individual particles confirm the distinctive nature of CB and EA activation. Strong supersaturation fluctuations induced by entrainment and turbulent mixing at cloud edges cause most EA particles to be deactivated soon after activation, substantially limiting their lifetime and growth relative to CB particles. Most net activation—the difference between activation and deactivation—occurs at the cloud base and vanishes aloft. Cloud droplet activation spectra follow the theoretical prediction at high supersaturation conditions, although the proportional constant is smaller because of particle deactivation. The spectra deviate from the theoretical prediction at low supersaturation conditions since they are affected by the transport of the CB particles activated elsewhere.

Chemical characterization, absolute configuration and optical purity of (1S)-(+)- and (1R)-(-)-10-camphorsulfonic acid.

Comprehensive chemical characterization for two isomers of camphorsulfonic acid (CSA), occasionally used in the manufacture of active pharmaceutical ingredients (APIs), was performed by nuclear magnetic resonance (NMR) spectroscopy, high-resolution mass spectroscopy in negative electrospray ionization mode and gas chromatography/mass spectrometry (GC/MS) in electron ionization mode. Electronic circular dichroism (ECD) spectra together with quantum chemical calculations using time-dependent density functional theory (TD-DFT) were used to assign the stereochemistry for CSA for the first time and these assignments were then confirmed by single-crystal X-ray diffraction. As crystals were grown under the same conditions of high supersaturation using a mixed solvent without water removal, the crystal structures of the two enantiomers contained one ordered molecule of water in the asymmetric unit. The crystals of the (+)-enantiomer have a 1S,4R configuration and the H atom of the sulfonic acid group combines with the water molecule to form a hydronium ion, namely, hydronium (1S,4R)-(7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonate, H3O+·C10H15O4S-. The crystals of the (-)-enantiomer have a 1R,4S configuration. The determination of the optical purity of CSA using NMR spectroscopy with a chiral solvating agent, (1R,2R)-1,2-diphenylethane-1,2-diamine, and GC/MS with a chiral column has been well explored. The results showed that the examined samples of these two isomers of CSA proved to be enantiomerically pure. In particular, for (1R)-(-)-10-camphorsulfonic acid, this is, to our knowledge, the first description on its spectral characterization in a scientific context.

Ultrascalable Surface Structuring Strategy of Metal Additively Manufactured Materials for Enhanced Condensation.

Metal additive manufacturing (AM) enables unparalleled design freedom for the development of optimized devices in a plethora of applications. The requirement for the use of nonconventional aluminum alloys such as AlSi10Mg has made the rational micro/nanostructuring of metal AM challenging. Here, the techniques are developed and the fundamental mechanisms governing the micro/nanostructuring of AlSi10Mg, the most common metal AM material, are investigated. A surface structuring technique is rationally devised to form previously unexplored two‐tier nanoscale architectures that enable remarkably low adhesion, excellent resilience to condensation flooding, and enhanced liquid–vapor phase transition. Using condensation as a demonstration framework, it is shown that the two‐tier nanostructures achieve 6× higher heat transfer coefficient when compared to the best filmwise condensation. The study demonstrates that AM‐enabled nanostructuring is optimal for confining droplets while reducing adhesion to facilitate droplet detachment. Extensive benchmarking with past reported data shows that the demonstrated heat transfer enhancement has not been achieved previously under high supersaturation conditions using conventional aluminum, further motivating the need for AM nanostructures. Finally, it has been demonstrated that the synergistic combination of wide AM design freedom and optimal AM nanostructuring method can provide an ultracompact condenser having excellent thermal performance and power density.

Role of Mass Transport in the Deposition, Growth, and Transformation of Calcium Carbonate on Surfaces at High Supersaturation.

We demonstrate how combined in-situ measurements and finite element method modeling can provide new insight into the relative contribution of mass transport to the growth of calcium carbonate on two model surfaces, glass and gold, under high-supersaturation conditions relevant to surface scaling. An impinging jet-radial flow system is used to create a high-supersaturated solution at the inlet of different cells: an optical microscope cell presenting a glass surface for deposition and quartz crystal microbalance (QCM) and in-situ IR spectroscopy cells, both presenting a gold surface. The approach described is quantitative due to the well-defined mass transport, and both time-lapse optical microscopy images and QCM data are analyzed to provide information on the growth kinetics of the calcite crystals. Initially, amorphous calcium carbonate (ACC), formed in solution, dominates the deposition process. At longer times, the growth of calcite is more significant and, on glass, is observed to consume ACC from the surface, leading to surface regions depleted of ACC developing around calcite microcrystals. On Au, the mass increase becomes linear with time in this region. Taken together, these microscopic and macroscopic measurements demonstrate that calcite growth has a significant component of mass transport control at high supersaturation. Finite element method (FEM) simulations of mass-transport-limited crystal growth support the strong mass transport contribution to the growth kinetics and further suggest that the observed growth must be sustained by more than just the Ca2+ and CO32– in solution, with dissolution/direct attachment of ACC and/or ion pairs also contributing to the growth process.

Comprehension of the Route for the Synthesis of Co/Fe LDHs via the Method of Coprecipitation with Varying pH.

Co/Fe-based layered double hydroxides (LDHs) are among the most promising materials for electrochemical applications, particularly in the development of energy storage devices, such as electrochemical capacitors. They have also been demonstrated to function as energy conversion catalysts in photoelectrochemical applications for CO2 conversion into valuable chemicals. Understanding the formation mechanisms of such compounds is therefore of prime interest for further controlling the chemical composition, structure, morphology, and/or reactivity of synthesized materials. In this study, a combination of X-ray diffraction, vibrational and absorption spectroscopies, as well as physical and chemical analyses were used to provide deep insight into the coprecipitation formation mechanisms of Co/Fe-based LDHs under high supersaturation conditions. This procedure consists of adding an alkaline aqueous solution (2.80 M NaOH and 0.78 M Na2CO3) into a cationic solution (0.15 M CoII and 0.05 M FeIII) and varying the pH until the desired pH value is reached. Beginning at pH 2, pH increases induce precipitation of FeIII as ferrihydrite, which is the pristine reactional intermediate. From pH > 2, CoII sorption on ferrihydrite promotes a redox reaction between FeIII of ferrihydrite and the sorbed CoII. The crystallinity of the poorly crystalized ferrihydrite progressively decreases with increasing pH. The combination of such a phenomenon with the hydrolysis of both the sorbed CoIII and free CoII generates pristine hydroxylated FeII/CoIII LDHs at pH 7. Above pH 7, free CoII hydrolysis proceeds, which is responsible for the local dissolution of pristine LDHs and their reprecipitation and then 3D organization into CoII4FeII2CoIII2 LDHs. The progressive incorporation of CoII into the LDH structure is accountable for two phenomena: decreased coulombic attraction between the positive surface-charge sites and the interlayer anions and, concomitantly, the relative redox potential evolution of the redox species, such as when FeII is re-oxidized to FeIII, while CoIII is re-reduced to CoII, returning to a CoII6FeIII2 LDH. The nature of the interlamellar species (OH−, HCO3−, CO32− and NO3−) depends on their mobility and the speciation of anions in response to changing pH.

Inhibition of CaCO3growth and synthesis of submicron particles by preferential adsorption of additive Ca2+ions on fresh precipitates

Method to inhibit CaCO3growth and synthesize submicron particles in a chemical precipitation process under ambient and high supersaturation conditions.

Ultra-fast growth of cuprate superconducting films: Dual-phase liquid assisted epitaxy and strong flux pinning

Cuprate superconductors are key candidate materials toward high energy-efficient devices. Improving their growth rate and performance under magnetic fields are indispensable for achieving even higher efficiency. For the first time, we demonstrated the ultra-high rate up to 100 nm/s in the growth of dual-phase cuprate superconducting film (EuBa2Cu3O7-BaHfO3). The growth rate achieved is two orders of magnitude higher than that at lab-scale and was also the highest on record to our best knowledge. Epitaxial growth mechanism assisted by the transient liquid phase is proposed, as evidenced by formation of Eu2BaCuO5 and Ba–Cu–O metastable phases under high supersaturation conditions. The high growth rate results in formation of mixed defective landscape, consisting of short nanorods, nanoparticles and naturally formed defects (e.g., staking faults). Due to such unique microstructure, we confirm that weak Jc anisotropy is dominated by random pinning mechanism. Contribution of isotropic and anisotropic Jc to Jctotal also varies with temperatures and magnetic field strength, which is a consequence of evolution of dominant pinning in film. As a result, the in-field current carrying capacity is significantly enhanced (exceeding 430 A/4 mm-width at 4.2 K, 18 T, B//c), being among the top tier of commercialized superconductor materials. This study establishes the correlation between ultra-high growth rate and flux pinning behaviors, which provides feasibility of dramatically improvement of production efficiency with the low price-performance ratio of future high temperature superconductor.

Crystal growth inhibition of gypsum under normal conditions and high supersaturations by a copolymer of phosphino-polycarboxylic acid

Scale formation is a bottleneck of most industrial and domestic water equipment, in particular, of oilfield water systems. Therefore, high-performance and environmentally-benign chemical scale inhibitors are highly needed. Phosphino-polycarboxylic acid (PPCA) is a low-in-phosphorous scale inhibitor with high inhibition efficiency, but its synthesis and performance analyses have been rarely disclosed. In this work for the first time, a PPCA copolymer is synthesized by a simple method based on free radical polymerization of acrylic acid and phosphinic acid monomers and directly employed for gypsum scale inhibition. The formation of PPCA was verified by FTIR and 31PNMR spectroscopies, and then its inhibition performance was evaluated by the complexometric determination of the Ca2+ concentration. The PPCA (2.5 ppm) showed 100% inhibition efficiency at a saturation index of 0.31 at the room temperature and without pH regulation after 24 h with practically no detectable gypsum crystallites even after two months, while the commercial ATMP showed a low inhibition efficiency of 30%. The Field Emission Scanning Microscopy (FESEM) images of the PPCA-inhibited and uninhibited samples revealed that the typical gypsum microfibers are distorted and reduced in size significantly in the inhibited sample. At a still higher saturation index of 1.47 (saturation ratio of 10), the inhibition efficiency of PPCA reduced to 16% and 24% for two dosages of 2.5 and 10 ppm which was attributed to the higher ion activity coefficients at the extremely high ionic strength, and hence, a much higher thermodynamic driving force. The rate constants for these two high supersaturation conditions and low PPCA dosages were also calculated and discussed.

In Vitro Coral Biomineralization under Relevant Aragonite Supersaturation Conditions.

The biomineralization of corals occurs under conditions of high and low supersaturation with respect to aragonite, which corresponds to day- or night-time periods of their growth, respectively. Here, in vitro precipitation of aragonite in artificial seawater was investigated at a high supersaturation, allowing spontaneous nucleation and growth, as well as at low supersaturation conditions, which allowed only the crystal growth on the deliberately introduced aragonite seeds. In either chemical systems, soluble organic matrix (SOM) extracted from Balanophyllia europaea (light sensitive) or Leptopsammia pruvoti (light insensitive) was added. The analyses of the kinetic and thermodynamic data of aragonite precipitation and microscopic observations showed that, at high supersaturation, the SOMs increased the induction time, did not affect the growth rate and were incorporated within aggregates of nanoparticles. At low supersaturation, the SOMs affected the aggregation of overgrowing crystalline units and did not substantially change the growth rate. On the basis of the obtained results we can infer that at high supersaturation conditions the formation of nanoparticles, which is typically observed in the skeleton's early mineralization zone may occur, whereas at low supersaturation the overgrowth on prismatic seeds observed in the skeleton fiber zone is a predominant process. In conclusion, this research brings insight on coral skeletogenesis bridging physicochemical (supersaturation) and biological (role of SOM) models of coral biomineralization and provides a source of inspiration for the precipitation of composite materials under different conditions of supersaturation.

Oxidation-assisted alkaline precipitation: the effect of H2O2 on the size of CuO and FeOOH nanoparticles.

H2O2 was demonstrated to narrow the size distribution and decrease the size of CuO and hydrous FeOOH (2-line ferrihydrite) nanoparticles under conditions of high supersaturation. We introduce oxidation-assisted alkaline precipitation (Ox-AP) and compare it to traditional alkaline precipitation (AP). While for AP, a metal salt solution (e.g., CuCl2) is mixed with an alkali (e.g., NaOH), for Ox-AP, the more reduced form of that metal salt solution (e.g., CuCl) is simultaneously mixed with that alkali and an oxidant (e.g., H2O2). The resulting precipitates were characterized with SEM, XRD, DLS and single particle ICP-MS and shown to be nanoparticles (NPs). Ox-AP CuO NPs were up to 3 times smaller than AP NPs. Ox-AP FeOOH NPs were up to 22.5% smaller than AP NPs. We discuss and propose a possible mechanism of Ox-AP through careful consideration of the known reaction chemistry of iron and copper. We propose that an increased monomer formation rate enhances the nucleation rate, which ultimately results in smaller particles with a more narrow distribution. The more distinct effect of Ox-AP on copper, was attributed to the fast formation of the stable CuO monomer, compared to AP, where the Cu(OH)2 and/or Cu2(OH)3Cl monomers are more likely formed. Although, the exact mechanism of Ox-AP needs experimental confirmation, our results nicely demonstrate the potential of using Ox-AP to produce smaller NPs with a more narrow distribution in comparison to using AP.

Gel formation of puerarin and mechanistic study during its cooling process

Recently, low molecular weight gelators are getting increasing interests in pharmaceutical field. In the current study, puerarin (PUE), a natural and bioactive flavonoid from the plant Pueraria lobata, was found to be able to gelate water to form hydrogel during cooling down process of its hot solution. In order to explore its gelation mechanism, the crystallization process, characterization, interaction force, morphology, rheological properties of PUE hydrogel were investigated by polarized light microscopy (PLM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Karl Fischer (KF), Raman spectrum, 1H-NMR, environmental scanning electron microscope (ESEM) and rheometer. The results indicated that at a high supersaturation condition, the gelation process of PUE was initiated by nucleation, and then fibers emanated rapidly from the nucleation center. The types of fiber growth changed from “fiber-like” growth to “less-linear” growth as the increase of supersaturation, leading to a denser structure with higher fractal dimension and stronger mechanical properties. Notably, the CO⋯π interaction facilitated the gelation assembly process, and the crystallographic mismatch branching played a vital role in constructing the network of PUE hydrogel.

The origin of the unique achondrite Northwest Africa 6704: Constraints from petrology, chemistry and Re–Os, O and Ti isotope systematics

Northwest Africa (NWA) 6704 is a unique achondrite characterized by a near-chondritic major element composition with a remarkably intact igneous texture. To investigate the origin of this unique achondrite, we have conducted a combined petrologic, chemical, and 187Re–187Os, O, and Ti isotopic study. The meteorite consists of orthopyroxene megacrysts (En55–57Wo3–4Fs40–42; Fe/Mn = 1.4) up to 1.7 cm in length with finer interstices of olivine (Fa50–53; Fe/Mn = 1.1–2.1), chromite (Cr# ∼ 0.94), awaruite, sulfides, plagioclase (Ab92An5Or3) and merrillite. The results of morphology, lattice orientation analysis, and mineral chemistry indicate that orthopyroxene megacrysts were originally hollow dendrites that most likely crystallized under high super-saturation and super-cooling conditions (1–102 °C/h), whereas the other phases crystallized between branches of the dendrites in the order of awaruite, chromite → olivine → merrillite → plagioclase. In spite of the inferred high super-saturation, the remarkably large size of orthopyroxene can be explained as a result of crystallization from a melt containing a limited number of nuclei that are preserved as orthopyroxene megacryst cores having high Mg# or including vermicular olivine. The Re–Os isotope data for bulk and metal fractions yield an isochron age of 4576 ± 250 Ma, consistent with only limited open system behavior of highly siderophile elements (HSE) since formation. The bulk chemical composition is characterized by broadly chondritic absolute abundances and only weakly fractionated chondrite-normalized patterns for HSE and rare earth elements (REE), together with substantial depletion of highly volatile elements relative to chondrites. The HSE and REE characteristics indicate that the parental melt and its protolith had not undergone significant segregation of metals, sulfides, or silicate minerals. These combined results suggest that a chondritic precursor to NWA 6704 was heated well above its liquidus temperature so that highly volatile elements were lost and the generated melt initially contained few nuclei of relict orthopyroxene, but the melting and subsequent crystallization took place on a timescale too short to allow magmatic differentiation. Such rapid melting and crystallization might occur as a result of impact on an undifferentiated asteroid. The O–Ti isotope systematics (Δ17O = −1.052 ± 0.004, 2 SD; ε50Ti = 2.28 ± 0.23, 2 SD) indicate that the NWA 6704 parent body sampled the same isotopic reservoirs in the solar nebula as the carbonaceous chondrite parent bodies. This is consistent with carbonaceous chondrite-like refractory element abundances and oxygen fugacity (FMQ = −2.6) in NWA 6704. Yet, the Si/Mg ratio of NWA 6704 is remarkably higher than those of carbonaceous chondrites, suggesting significant nebular fractionation of forsterite in its provenance.

SYNTHESIS OF HYDROTALCITE POWDER AND BEAD TO REMOVE ARSENATE

The affecting factors on the synthesis of hydrotalcite (HT) powder and bead for effective arsenate removal were investigated. HTs with a ratio of Mg:Al = 2:1 (MA) were synthesized by the co-precipitation method at 70 oC with reaction times of 1 and 120 - 300 min. The synthesis of MA with a reaction time of 1 min was done under high supersaturation condition, the others under low supersaturation conditions. The characteristics of MA were examined by X-ray diffraction (XRD), scanning electron microscopy, and nitrogen adsorption/desorption isotherms. According to the XRD patterns, pure HT was obtained for all tested conditions. With increasing reaction time from 1 to 300 min, the crystal size of MA increased from 4.9 to 11.3 μm, the surface area of MA increased from 9.3 to 71.4 m2/g. Batch-mode experiments showed that 1-min reaction time MA had the highest As(V) removal capacity. MA beads were separately synthesized using alginate and poly acrylamide (PAM) as binding agents. For alginate/MA, heat drying (110 oC) and freeze drying were applied to test the effect of these drying methods on the beads. The results showed that As(V) adsorption capacity of PAM/MA was the highest, closely followed by freeze drying/alginate/MA, much higher than that of heat drying/alginate/MA bead.

Origin and effective reduction of inversion domains in aluminum nitride grown by a sublimation method

Owing to the large differences in the chemical properties between Al and N polarities in aluminum nitride (AlN), the choice of the polar direction for crystal growth strongly affects not only the quality but also the shape (facet formation) of the grown crystal. In particular, N-polar (000−1) has been considered to be a more preferable direction than Al-polar (0001) for sublimation growth because compared to Al-polar (0001), N-polar (000−1) exhibits better stability at high growth rate (high supersaturation) conditions and enables easier lateral enlargement of the crystal. However, some critical growth conditions induce polarity inversion and hinder stable N-polar growth. Furthermore, the origin of the polarity inversion in AlN growth by the sublimation method is still unclear. To ensure stable N-polar growth without polarity inversion, the formation mechanism of the inversion domain during AlN sublimation growth must be elucidated. Therefore, herein, we demonstrate homoepitaxial growth on an N-polar seed and carefully investigate the obtained crystal that shows polarity inversion. Annular bright-field scanning transmission electron microscopy reveals that polarity is completely converted to the Al polarity via the formation of a 30nm thick mixed polar layer (MPL) just above the seed. Moreover, three-dimensional atom probe tomography shows the segregation of the oxygen impurities in the MPL with a high concentration of about 3atom%. Finally, by avoiding the incorporation of oxygen impurity into the crystal at the initial stage of the growth, we demonstrate an effective reduction (seven orders of magnitude) of the inversion domain boundary formation.

An improved model of homogeneous nucleation for high supersaturation conditions: aluminum vapor.

A novel model of stationary nucleation, treating the thermodynamic functions of small clusters, has been built. The model is validated against the experimental data on the nucleation rate of water vapor obtained in a broad range of supersaturation values (S = 10-120), and, at high supersaturation values, it reproduces the experimental data much better than the traditional classical nucleation model. A comprehensive analysis of the nucleation of aluminum vapor with the usage of developed stationary and non-stationary nucleation models has been performed. It has been shown that, at some value of supersaturation, there exists a double potential nucleation barrier. It has been revealed that the existence of this barrier notably delayed the establishment of a stationary distribution of subcritical clusters. It has also been demonstrated that the non-stationary model of the present work and the model of liquid-droplet approximation predict different values of nucleation delay time, τs. In doing so, the liquid-droplet model can underestimate notably (by more than an order of magnitude) the value of τs.

The Year Leading to a Supereruption.

Supereruptions catastrophically eject 100s-1000s of km3 of magma to the surface in a matter of days to a few months. In this study, we use zoning in quartz crystals from the Bishop Tuff (California) to assess the timescales over which a giant magma body transitions from relatively quiescent, pre-eruptive crystallization to rapid decompression and eruption. Quartz crystals in the Bishop Tuff have distinctive rims (<200 μm thick), which are Ti-rich and bright in cathodoluminescence (CL) images, and which can be used to calculate Ti diffusional relaxation times. We use synchrotron-based x-ray microfluorescence to obtain quantitative Ti maps and profiles along rim-interior contacts in quartz at resolutions of 1–5 μm in each linear dimension. We perform CL imaging on a scanning electron microscope (SEM) using a low-energy (5 kV) incident beam to characterize these contacts in high resolution (<1 μm in linear dimensions). Quartz growth times were determined using a 1D model for Ti diffusion, assuming initial step functions. Minimum quartz growth rates were calculated using these calculated growth times and measured rim thicknesses. Maximum rim growth times span from ~1 min to 35 years, with a median of ~4 days. More than 70% of rim growth times are less than 1 year, showing that quartz rims have mostly grown in the days to months prior to eruption. Minimum growth rates show distinct modes between 10−8 and 10−10 m/s (depending on sample), revealing very fast crystal growth rates (100s of nm to 10s of μm per day). Our data show that quartz rims grew well within a year of eruption, with most of the growth happening in the weeks or days preceding eruption. Growth took place under conditions of high supersaturation, suggesting that rim growth marks the onset of decompression and the transition from pre-eruptive to syn-eruptive conditions.

Effect of Cu-ZnO-Al2O3 supported on H-ferrierite on hydrocarbons formation from CO hydrogenation

Methanol synthesis catalysts based on Cu, Zn and Al were prepared by three methods and subsequently mixed with H-ferrierite zeolite in an aqueous suspension to disperse the catalysts over the support. These materials were characterized by X-ray diffraction, N2 adsorption, transmission electron microscopy, temperature programmed reduction, NH3 and H2 temperature-programmed desorption, and X-ray photoelectron spectroscopy. They were also applied to the CO hydrogenation reaction to produce dimethyl ether and hydrocarbons. The catalysts were prepared by coprecipitation under low and high supersaturation conditions and by a homogeneous precipitation method. The preparation technique was found to affect the precursor structural characteristics, such as purity and crystallinity, as well as the particle size distribution of the resulting catalyst. Low supersaturation conditions favored high dispersion of the Cu species, increasing the methanol synthesis catalyst's metallic surface area and resulting in a homogeneous particle size distribution. These effects in turn were found to modify the zeolite properties, promoting both a low micropore volume and blockage of the zeolite acid sites. The effect of the methanol synthesis catalyst on the reaction was verified by the correlation between the Cu surface area and the CO conversion rate.

Effect of CaCO3(S) Nucleation Modes on Algae Removal from Alkaline Water.

The role of calcite heterogeneous nucleation was studied in a particle-coagulation treatment process for removing microalgae from water. Batch experiments were conducted with Scenedesmus sp. and Chlorella sp. in the presence and absence of carbonate and in the presence and absence of magnesium to delineate the role of CaCO3(S) nucleation on microalgae removal. The results indicate that effective algae coagulation (e.g., up to 81% algae removal efficiency) can be achieved via heterogeneous nucleation with CaCO3(S); however, supersaturation ratios between 120 and 200 are required to achieve at least 50% algae removal, depending on ion concentrations. Algae removal was attributed to the adsorption of Ca2+ onto the cell surface, which provides nucleation sites for CaCO3(S) precipitation. Bridging of calcite particles between the algal cells led to rapid aggregation and formation of larger flocs. However, at higher supersaturation conditions, algae removal was diminished due to the dominance of homogeneous nucleation of CaCO3(S). The removal of algae in the presence of Ca2+ and Mg2+ required higher supersaturation values; however, the shift from heteronucleation to homonucleation with increasing supersaturation was still evident. The results suggest that water chemistry, pH, ionic strength, alkalinity, and Ca2+ concentration can be optimized for algae removal via coagulation and sedimentation.

Morphology control of BiFeO3aggregatesviahydrothermal synthesis

The assembly of crystalline building units with specific shape-derived properties into aggregates is often required to broaden their practical applications because the properties of the building units can be fully integrated and used in the aggregates owing to their orientation. Herein, morphology-controlled BiFeO3aggregates composed of oriented crystalline building units were fabricatedviaa hydrothermal process without any additives, and the effects of the supersaturation conditions on the aggregation state were investigated. The supersaturation condition, controlled by varying the KOH concentration, was found to affect the shape of the crystalline building units. For lower supersaturation conditions, the morphology of the aggregates was found to be closely related to the shape of the fundamental building units, and the results indicated that oriented attachment occurred between specific crystal faces of the building units. Under a high supersaturation condition, the morphology of the aggregate did not reflect the shape of the building units and a monodispersed spherical aggregate was obtained. Further, the internal microstructures of the aggregates changed from homogeneous and dense to sparse core and dense shell structures with an increasing supersaturation condition. The formation mechanism of these morphology-controlled aggregates is discussed using microstructure analyses. The present approach to control the morphology of aggregates using the shape of the building units and aggregation kinetics could also be applicable for other microcrystalline aggregated systems in addition to BiFeO3.

Simultaneous Measurement of CCN Activity and Chemical Composition of Fine-Mode Aerosols at Noto Peninsula, Japan, in Autumn 2012

Size resolved CCN activity and bulk chemical composition of atmospheric aerosols in the submicrometer size range were measured at Noto Ground-based Research Observatory (NOTOGRO), facing the Sea of Japan at the tip of Noto Peninsula, in autumn 2012. In the atmospheric measurement, the CCN efficiency spectra, where the CCN number fraction is plotted against the diameter of aerosols, were obtained for four different supersaturation (SS) conditions. The hygroscopicity parameter κ, which depends on the chemical composition of aerosols, was estimated from analysis of the CCN spectra. The CCN activation diameters of ambient aerosols were clearly larger than those of pure ammonium sulfate under all SS conditions. The bulk chemical composition derived by an aerosol chemical speciation monitor (ACSM) also indicated the significant mass fraction of organics in the submicrometer size range. The relationship between the estimated κ values and the CCN activation diameters suggests that organics contribute the aerosol mass especially in the size range of less than 100 nm. The contribution of organics observed in this study was more apparent than those of other sites in East Asia. The mass concentrations and chemical compositions of the aerosols varied with trajectory pathway, which caused large fluctuations in κ values especially at higher SS conditions. The negative correlations between organic mass fraction and the diameters of cloud droplet diameters were observed under low SS conditions (0.13% and 0.25%), suggesting that less-hygroscopic organics, that can suppress the initial growth rates of cloud droplets, were included during the periods of large organic mass concentrations.