Supersaturation Concentration Research Articles

Environmental drivers of seasonal and hourly fluxes of methane and carbon dioxide across a lowland stream network with mixed catchment

Streams serve as open windows for carbon emissions to the atmosphere due to the frequent supersaturation of carbon dioxide (CO2) and methane (CH4) that originates from large carbon input during runoff and associated in-stream processes. Due to the high spatial and temporal variability of the underlying environmental drivers (e.g., concentrations of dissolved CO2 and CH4, turbulence, and temperature), it has remained difficult to address the importance and upscale the emissions to annual whole-system and regional values. In this study, we measured concentrations and calculated emissions of CO2 and CH4 at diel and seasonal scales at 15 stations in a 1.4 km2 stream network that drains a mixed lowland catchment consisting of agriculture (210 km2), forest (56 km2), and lakes, ponds, and wetlands (22 km2) in the upper River Odense, Denmark to evaluate environmental drivers behind the spatiotemporal variability. We used automatically venting floating chambers to calculate hourly diffusive fluxes of CO2 and CH4 and CH4 ebullition. We found: 1) highly supersaturated CO2 and CH4 concentrations (median: 175 and 0.33 µmol L−1, respectively) and high diffusive fluxes of CO2 and CH4 (median: 3,608 and 19 µmol m−2 h−1, respectively); 2) lower daytime than nighttime diffusive emissions of CO2 in spring and summer, but no diel variability of CH4; 3) higher concentrations and emissions of CH4 at higher temperatures; and 4) higher emissions of CH4 at stations located in sub-catchments with higher agricultural coverage. Ebullition of CH4 peaked at two stations with soft organic sediment and low summer flow, and their ebullition alone constituted 30% of total annual CH4 emissions from the stream network. Mean annual CO2 emissions from the hydrological network (37.15 mol CO2 m−2 y−1) exceeded CH4 emissions 100-fold (0.43 mol CH4 m−2 y−1), and their combined warming potential was 1.83 kg CO2e m−2 y−1. Overall, agricultural sub-catchments had higher CH4 emissions from streams, while lakes and ponds likely reduced downstream CH4 and CO2 emissions. Our findings demonstrate that CO2 and CH4 emissions data at high spatial and temporal resolution are essential to frame the heterogeneous stream conditions, understand gas emissions regulation, and upscale to annual values for hydrological networks and larger regions.

ECoral: How Electrolysis Could Restore Seawater Conditions Ideal for Coral Reefs.

Coral reefs suffer from climate change, including long-term ocean acidification (OA) and warming and short-term bleaching, tropical storms, and pollution events, all of which are increasing in frequency and severity. It is urgent yet unclear how to intervene to save coral reefs. Reversal of the ocean pH to preindustrial levels could restore coral reefs to their preindustrial growth rates; however, strategies to reverse OA on environmentally relevant scales have not been established. Anecdotally, electrolysis seems to help coral reefs recover from acidification and short-term events, but few uncontrolled studies support such claims. Here, using two independent continuum simulation approaches (COMSOL and CrunchFlow), we show the effect of electrolysis on seawater chemistry relevant to coral reef survival and growth. We conclude that near the negative electrodes, the cathodes, seawater pH, supersaturation, and carbonate concentration all increase significantly. Electrolysis of seawater, therefore, can be used to restore preindustrial ocean conditions locally to save coral reefs, an approach termed eCoral here. We anticipate these simulation results to be the starting point for controlled experiments to test whether seawater electrolysis promotes coral reef growth and restoration, as these simulations predict.

Mechanisms of dissolution and crystallization of amorphous glibenclamide

Amorphous solid dispersions enhance the dissolution and oral bioavailability of poorly water-soluble drugs. However, the link between polymer properties and formulation performance has not been fully clarified yet. We studied the effect of hydroxypropyl cellulose (HPC) polymers molecular weight (Mw) on the storage stability, dissolution kinetics and supersaturation stability of spray-dried amorphous glibenclamide (GLB) formulations. The solid-state stability of amorphous GLB during storage was significantly enhanced by both the 40 kDa (HPC-SSL) and 84 kDa (HPC-L) polymers, regardless of Mw differences. In contrast, HPC-SSL maintained significantly higher aqueous drug concentrations during dissolution, compared to HPC-L (its higher Mw analogue). Dedicated dissolution experiments, in situ optical microscopy and solid-state characterization revealed that aqueous drug concentrations were determined by the interplay between crystallization inhibition, drug ionization, wetting and solubilization effects: (1) HPC prevents surface nucleation, hence inhibiting crystallization, (2) intestinal colloids (bile salts and phospholipids) increase supersaturated drug concentrations via wetting and solubilization effects and (3) pH and drug ionization severely impact the degree of supersaturation. The better performance of the lower Mw HPC-SSL was due to its superior inhibition of surface crystallization during dissolution. These insights into the molecular mechanisms of dissolution and crystallization of amorphous solids provide foundation for rational formulation development.

Microfluidic Laser-Induced Nucleation of Iron (II,III) Oxide Nanoparticle-Doped Supersaturated Aqueous KCl Solutions.

A capillary-based microfluidic system designed for nonphotochemical laser-induced nucleation (NPLIN) studies coupled with real-time microscopy was used to study NPLIN of iron (II,III) oxide doped aqueous KCl solutions. Supersaturation was achieved by lowering the solution temperature using thermoelectric cooling, and heating was used for the dissolution of crystals downstream to prevent clogging during the flow. The effect of nanoparticle concentration, supersaturation, laser intensity, and filtration was studied. We report laser-induced nucleation using laser intensities as low as 1 MW/cm2 with nanoparticle number densities of ∼109 particles per mL of solution at KCl supersaturations from 1.06 to 1.08. The number of crystals increased with increasing laser intensity, supersaturation, and nanoparticle concentration. We discuss our results with respect to the colloidal impurity-heating mechanism hypothesis and propose a semiempirical model based on the nanoparticle heating and bubble formation due to the absorption of laser energy.

Short-lived calcium carbonate precursors observed in situ via Bullet-dynamic nuclear polarization

The discovery of (meta)stable pre-nucleation species (PNS) challenges the established nucleation-and-growth paradigm. While stable PNS with long lifetimes are readily accessible experimentally, identifying and characterizing early-stage intermediates with short lifetimes remains challenging. We demonstrate that species with lifetimes ≪ 5 s can be characterized by nuclear magnetic resonance spectroscopy when boosted by ‘Bullet’ dynamic nuclear polarization (Bullet-DNP). We investigate the previously elusive early-stage prenucleation of calcium carbonates in the highly supersaturated concentration regime, characterizing species that form within milliseconds after the encounter of calcium and carbonate ions and show that ionic pre-nucleation species not only govern the solidification of calcium carbonates at weak oversaturation but also initiate rapid precipitation events at high concentrations. Such, we report a transient co-existence of two PNS with distinct molecular sizes and different compositions. This methodological advance may open new possibilities for studying and exploiting carbonate-based material formation in unexplored parts of the phase space.

One-step synthesis and characterization of Y2O3 nanoparticles via emulsion detonation method

Yttrium oxide (Y2O3) nanoparticles have critical applications in many industries, including ceramics, optics, and biomedicine. However, conventional synthesis methods are typically cumbersome and time-consuming. Herein, a novel emulsion detonation method successfully achieved the one-step synthesis of Y2O3 nanoparticles. In this method, yttrium nitrate hexahydrate was uniformly dispersed in the emulsion explosive as a precursor and an auxiliary oxidizer. After the emulsion explosive was detonated in a detonation chamber, the detonation products were collected, purified and characterized by X-ray diffraction, Fourier transform infrared spectrometer, Raman spectrometer, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, field emission transmission electron microscopy, and ultraviolet spectrophotometer. The results show that the as-synthesized powders are high-purity cubic phase yttrium oxide nanoparticles with a spherical-like morphology and an average particle size of approximately 30 nm. These Y2O3 nanoparticles have a wide (5.53 eV) energy band gap, close to the conventional methods. Based on detonation theory, thermochemical theory, and characterization results, this text discussed the mechanism of the Y2O3 nanoparticles synthesized by the emulsion detonation method. During detonation, the formation of the Y2O3 nanoparticles underwent three stages: the formation of the Y2O3 molecules by the collision of Y and O ions, the formation of the crystal nucleus at supersaturation concentration, and crystal growth. This study provides a novel, cost-effective method for efficiently synthesizing Y2O3 nanoparticles.

The Assessment of Pit Chemistry Parameters of 316 Stainless Steel and 304 Stainless Steel by Adding a Molybdate Inhibitor in a Chloride Aggressive Media

In this study, the efficacy of Mo as an alloying element and inhibitor on the pit chemistry parameters of 316 stainless steel (316SS) (2 wt% Mo) and 304 stainless steel (304SS) (0.2 wt% Mo) in chloride and molybdate-bearing solution is investigated. To evaluate pit chemistry parameters, three-step polarization and four-step polarization tests using a pencil electrode were conducted. The results suggested that the presence of molybdate ions increased the pit transition potential and repassivation potential. Moreover, molybdate increases the critical, saturation, and supersaturation concentrations at an equal pit depth. Therefore, the concentration of necessary cations increased to precipitate the salt. A comparison of the pit chemistry characteristics between 316SS and 304SS showed that molybdenum increased the potential necessary for salt removal and facilitated the repassivation process of the individual pit.

Deformation mechanisms and mechanical properties of the high-strength and ductile Al-Zn-Mg-Cu alloys processed by repetitive continuous extrusion forming process with different heat treatments

Continuous severe plastic deformation (SPD) processes, which overcome the limitations of economic efficiency and sample size for classical SPD approaches, are promising industry technologies for manufacturing aluminum alloy products with refined microstructures and enhanced properties. In the present work, the repetitive continuous extrusion forming (R-Conform) process combined with auxiliary thermal treatments was implemented in Al-Zn-Mg-Cu alloys, which had poor workability. By combining microstructural observation, mechanical testing and finite element simulation, the influence of auxiliary heat treatments on the mechanisms of grain refinement and strengthening for Al-Zn-Mg-Cu alloys processed by R-Conform were systematically investigated. The results indicated that the grains of Al-Zn-Mg-Cu alloys were significantly refined by a continuous dynamic recrystallization (CDRX) during the R-Conform process with special thermomechanical conditions. The increased supersaturated solid solution concentration and constituent precipitate fraction caused by prehomogenization were found to accelerate CDRX for grain refinement through the pinning effect on dislocation motion. Due to the simultaneous effect of shear deformation and online solution, the R-Conformed alloys contained massive lattice distortions and high concentrations of solute atoms. As a result, the processed Al-Zn-Mg-Cu alloys combined with prehomogenization and direct aging treatments possibly possess a good combination of strength and ductility due to the integrated functions of fine grains, massive lattice distortion, and evenly distributed nanosized precipitates.

Optimisation of Pharmaceutical Cocrystal Dissolution Performance through a Synergistic Precipitation Inhibition

ObjectivesPolymeric excipients play an important role in a cocrystal formulation to act as precipitation inhibitors to maximize the potential. Otherwise, a stable form of the parent drug will be recrystallized on the dissolving cocrystal surface and/or in the bulk solution during the cocrystal dissolution process, negating the solubility advantage. The objectives of this work were to investigate the potential of using combined polymers to maximise the dissolution performance of surface precipitation pharmaceutical cocrystals.MethodsThe dissolution performance of a highly soluble flufenamic acid and nicotinamide (FFA-NIC) cocrystal has been systematically studied with predissolved or powder mixed with a single polymer, including a surface precipitation inhibitor [i.e., copolymer of vinylpyrrolidone (60%) /vinyl acetate (40%) (PVP-VA)] and two bulk precipitation inhibitors [i.e., polyethylene glycol (PEG) and Soluplus (SLP)], or binary polymers combinations.ResultsA single polymer of PVP-VA prevented the FFA surface precipitation for an enhanced dissolution performance of FFA-NIC cocrystal. Unfortunately, it cannot sustain the supersaturated FFA concentration in the bulk solution. A combination of two polymers of PVP-VA and SLP has shown a synergistic inhibition effect to enhance the dissolution advantage of FFA-NIC cocrystal.ConclusionsThe dissolution of a cocrystal with surface precipitation of the parent drug can be described as: i) the cocrystal surface contacting the dissolution medium; ii) the cocrystal surface dissolving; iii) the parent drug precipitation on the dissolving surface; and iv) the parent drug particles redissolving. A combination of two types of polymers can be used to maximise the cocrystal performance in solution.Graphical

Size-dependent hygroscopicity of levoglucosan and D-glucose aerosol nanoparticles

Abstract. The interaction between water vapor and aerosol nanoparticles is important in atmospheric processes. Hygroscopicity of sub-10 nm organic nanoparticles and their concentration-dependent thermodynamic properties (e.g., water activity) in the highly supersaturated concentration range are, however, scarcely available. Here we investigate the size dependence of hygroscopicity of organics (i.e., levoglucosan, D-glucose) in dry particle diameter down to 6 nm using a nano-hygroscopicity tandem differential mobility analyzer (nano-HTDMA). Our results show that there is only weak size-dependent hygroscopic growth of both levoglucosan and D-glucose nanoparticles with diameters down to 20 nm. In the diameter range smaller than 20 nm (down to 6 nm), we observed strong size-dependent hygroscopic growth for D-glucose nanoparticles. The hygroscopic growth factors cannot be determined for levoglucosan below 20 nm due to its evaporation. In addition, we compare hygroscopicity measurements for levoglucosan and D-glucose nanoparticles with E-AIM (standard UNIFAC – functional group activity coefficients), the ideal solution theory, and differential Köhler analysis (DKA) predictions. The ideal solution theory describes the measured hygroscopic growth factors of levoglucosan with diameters down to 20 nm and D-glucose nanoparticles with diameters larger than 60 nm, while E-AIM (standard UNIFAC) can successfully predict the growth factors of D-glucose nanoparticles with diameters from 100 down to 6 nm at RH above 88 %–40 % (e.g., at RH above 88 % for 100 nm D-glucose, at RH above 40 % for 6 nm D-glucose). The use of the DKA method leads to good agreement with measured hygroscopic growth factors of D-glucose aerosol nanoparticles with diameters from 100 down to 6 nm. Predicted water activity for these aqueous organic solutions (i.e., levoglucosan, D-glucose) from different parameterization methods agrees well with observations in the low solute concentration range (< 20 mol kg−1) and starts to deviate from observations in the high solute concentration (> 20 mol kg−1).

Role of ionic diffusion in heat flow and chemical shrinkage of tricalcium aluminate hydration subjected to thermo-chemo-electrical coupled fields

The role of ion diffusion in the heat flow and chemical shrinkage of tricalcium aluminate (C3A) hydration was investigated using the proposed multi-ionic reactive transport model for C3A hydration. Ion diffusion, dissolution, and precipitation reactions were coupled in the governing equation of the chemical field during C3A hydration in the presence of gypsum. Ion diffusion and chemical reactions were also governed by the electric and temperature fields in the model. Theoretical computations were performed relating ion diffusion to heat flow and chemical shrinkage during all stages of C3A hydration. Excellent agreement was achieved by comparing the simulation results and the experimental data under various conditions. The effects of the gypsum content, specific surface area (SSA), and curing temperature on the ion diffusion, electrical potential, heat flow, and chemical shrinkage were numerically studied. The results indicated that (1) higher gypsum contents, SSAs, and curing temperatures increased the ion concentration gradient and improved the supersaturation concentration of sulfate near the C3A surface; (2) higher gypsum contents led to faster decreases in the Ca2+ and SO42− concentrations before the depletion of gypsum; and (3) the gypsum content affected the phase assemblage through spatial and temporal evolution of the ionic species. The proposed model may guide the design of the C3A-gypsum system and can be extended to optimize the fluidity and setting properties of the cement paste.

Towards reliable retrievals of cloud droplet number for non-precipitating planetary boundary layer clouds and their susceptibility to aerosol

Remote sensing has been a key resource for developing extensive and detailed datasets for studying and constraining aerosol-cloud-climate interactions. However, aerosol-cloud collocation challenges, algorithm limitations, as well as difficulties in unraveling dynamic from aerosol-related effects on cloud microphysics, have long challenged precise retrievals of cloud droplet number concentrations. By combining a series of remote sensing techniques and in situ measurements at ground level, we developed a semi-automated approach that can address several retrieval issues for a robust estimation of cloud droplet number for non-precipitating Planetary Boundary Layer (PBL) clouds. The approach is based on satellite retrievals of the PBL cloud droplet number (Ndsat) using the geostationary meteorological satellite data of the Optimal Cloud Analysis (OCA) product, which is obtained by the Spinning Enhanced Visible and InfraRed Imager (SEVIRI) of the European Organization for the Exploitation of Meteorological Satellites (EUMETSAT). The parameters of the retrieval are optimized through closure with droplet number obtained from a combination of ground-based remote sensing data and in situ observations at ground level. More specifically, the remote sensing data are used to retrieve cloud-scale vertical velocity, and the in situ aerosol measurements at ground level were used constrain as input to a state-of-the-art droplet activation parameterization to predict the respective Cloud Condensation Nuclei (CCN) spectra, cloud maximum supersaturation and droplet number concentration (Nd), accounting for the effects of vertical velocity distribution and lateral entrainment. Closure studies between collocated Nd and Ndsat are then used to evaluate exising droplet spectral width parameters used for the retrieval of droplet number, and determine the optimal values for retrieval. This methodology, used to study aerosol-cloud interactions for non-precipitating clouds formed over the Athens Metropolitan Area (AMA), Greece from March to May 2020, shows that droplet closure can be achieved to within 30%, comparable to the level of closure obtained in many in situ studies. Given this, the ease of applying this approach with satellite data obtained from SEVIRI with high temporal (15 min) and spatial resolution (3.6 km × 4.6 km), opens the possibility of continuous and reliable Ndsat, giving rise to high value datasets for aerosol-cloud-climate interaction studies.

Modelling dynamic precipitation in pre-aged aluminium alloys under warm forming conditions

This work presents a model for deformation enhanced precipitate growth and coarsening kinetics in pre-aged 7xxx aluminium alloys under warm forming conditions (100 to 200 °C). A multi-class Kampmann–Wagner framework is used to describe the evolution of precipitate size distribution, where the effect of deformation is incorporated through enhanced solute diffusivity resulting from deformation induced excess vacancies. A classical phenomenological model is used to describe the accumulation of excess vacancies. The model is validated with experimental warm deformation data from the literature, and applied to investigate a wide range of deformation conditions to predict the effect of strain, strain rate and temperature on precipitate growth and coarsening kinetics. It is demonstrated that the interaction of solute supersaturation and excess vacancy concentration can lead to complex non-monotonic precipitate growth rate variation for certain regimes of strain rate and temperature.

Maritime Aerosol and CCN Profiles Derived From Ship‐Based Measurements Over Eastern North Pacific During MAGIC

AbstractAtmospheric aerosols are widely recognized to give rise to a substantial radiative forcing to the climate by scattering and absorbing radiation and by modifying the microphysical, lifetime, and radiative properties of clouds. During the Marine ARM GPCI Investigation of Clouds (MAGIC) over the Eastern North Pacific (ENP), the ship‐based measured cloud condensation nuclei (CCN) concentration at 0.2% supersaturation (NCCN,0.2) and condensation nuclei concentration (NCN) had mean values of 116.7 and 219.4 cm−3, with the highest concentrations found closest to LA due to an increase in aerosol sources. Moving westward, both NCCN,0.2 and NCN gradually decreased until stabilizing near 100 cm−3 and 200 cm−3, respectively. Using the methods proposed by Ghan and Collins (2004), https://doi.org/10.1175/1520-0426(2004)021<0387:uoisdt>2.0.co;2 and Ghan et al. (2006), https://doi.org/10.1029/2004jd005752, NCCN,0.2 profiles are retrieved using the surface measured NCCN,0.2 as a constraint. For coupled conditions, correlations between the retrieved NCCN,0.2 profiles and cloud‐droplet number concentration (NC) increase from 0.26 at the surface to 0.38 near cloud base, particularly true for non‐drizzling clouds. Although the correlations are lower than expected, the percentage increase (46.2%) is encouraging. Finally, the relationships between cloud breakup (CB) and the stratocumulus to cumulus transition (SCT) with environmental conditions and associated aerosols are also studied. The decreased NCN trend east of CB is mainly caused by precipitation scavenging, while the increased NCN trend west of CB is strongly associated with the increased surface wind speed and fewer drizzle events. A further study is needed using high‐resolution models to simulate these events.

Heat treatment of hot-isostatic-pressed 60NiTi shape memory alloy: Microstructure, phase transformation and mechanical properties

60NiTi alloy is considered to be a promising material for specialized bearing and gear applications due to its high hardness, strength, and low modulus. However, fabricating 60NiTi through conventional processing methods is challenging due to the brittleness and poor workability. In this study, 60NiTi with high relative density was successfully fabricated directly from pre-alloyed powder through hot isostatic pressing. The effects of solution and aging treatments on microstructure and mechanical properties were systematically studied by advanced characterization techniques. The hot-isostatic-pressed 60NiTi showed low average hardness and elastic strain due to the formation of a soft Ni3Ti phase and B2 NiTi matrix. Solution treatment above 1000 °C dissolved the Ni3Ti phase and promoted the formation of nanoscale Ni4Ti3 precipitates, which significantly improved the hardness, strength, and elastic strain of 60NiTi. The formation of the Ni4Ti3 phase can be mainly attributed to the driving forces induced by the chemical supersaturation and mechanical stress concentration. Finally, the phase transformation mechanisms during heat treatment and compression test were discussed.

Hot-melt extruded hydroxypropyl methylcellulose acetate succinate based amorphous solid dispersions: Impact of polymeric combinations on supersaturation kinetics and dissolution performance

Nucleation inhibition and maintenance of drug supersaturation over a prolonged period are desirable for improving oral absorption of amorphous solid dispersions. The present study investigates the impact of binary and ternary amorphous solid dispersions on the supersaturation kinetics of nifedipine using the polymers hydroxypropylmethylcellulose acetate succinate (HPMCAS) LG, and HG, Eudragit® RSPO, Eudragit® FS100, Kollidon® VA64 and Plasdone™ K-29/32. The amorphous solubility, nucleation induction time, and particle size analysis of nifedipine in a supersaturated solution were performed with and without the presence of polymers, alone or in combination. The HPMCAS-HG and HPMCAS-HG + LG combinations showed the highest nifedipine amorphous solubility of 169.47, 149.151 µg/mL, respectively and delay in nucleation induction time up to 120 min compared to other polymeric combinations. The solid dispersions prepared via hot melt extrusion showed the transformation of crystalline nifedipine to amorphous form. The in-vitro non-sink dissolution study revealed that although the binary nifedipine/HPMCAS-LG system had shown the greater supersaturation concentration of 66.1 µg/mL but could not maintain a supersaturation level up to 360 min. A synergistic effect emerged for ternary nifedipine/HPMCAS-LG/HPMCAS-HG, and nifedipine/HPMCAS-LG/Eudragit®FS100 systems maintained the supersaturation level with enhanced dissolution performance, demonstrating the potential of polymeric combinations for improved amorphous solid dispersion performance.

Thermodynamic Study on the Amorphous Form and Crystalline Hydrates Using in Situ Raman and FBRM

AbstractThe solubilities and maximum supersaturation concentrations of an amorphous and the crystalline tetrahydrate and heptahydrate solids of disodium guanosine 5'‐monophosphate (GMP) in water‐methanol mixtures were measured in situ by Raman spectroscopy and focused beam reflectance measurement. The distinct Raman peaks of the amorphous form, crystalline hydrates, solution, and solvent were used for measurements of solubility and maximum supersaturation. Above 45 °C and at methanol fractions of 0.15–0.90, the tetrahydrate was the stable form, while below 40 °C and at methanol fractions of 0.15–0.60, the heptahydrate was the stable form. Especially, the tetrahydrate was stable in the methanol fraction > 0.7 at the temperature investigated. The solubility and supersaturated concentration values can be used to selectively produce amorphous, tetrahydrate, and heptahydrate solids of GMP by anti‐solvent crystallization.

Organic Removal Treatment Using Microbubble Generator (MBG) in Eutrophic Disorder Condition

The Techno Park basin, built as an extension of a small tributary of the Code River primarily acts as a retention basin for runoff during the rainy season. It improves the quality of water that has been degraded by domestic wastewater discharge from the surrounding community. Therefore, this study aims to assess the extent to which water quality of the basin can be improved with aeration technology. The aeration technology is a Microbubble Generator (MBG) built using a 100 Watts submersible pump with three horizontal nozzles at a depth of 40 cm from the water surface. Furthermore, the profiles of dissolved oxygen (DO) concentration were measured at the basin’s inlet and outlet, as well as the depths of 1 m below surface water and the bottom of the basin. Diurnal DO was measured to investigate the causes of supersaturation. The aeration performance was also determined from the COD parameters at the inlet and outlet. Discharge measurements were then conducted on the tributary/drainage channel to the inlet basin. The result showed that the DO supersaturation concentration has been attributed to the contribution of photosynthesis from phytoplankton such as algae. Furthermore, no change in DO concentration was observed in a range of 1 m depth from the surface of the water to the bottom (0.3 - 0.14 mg-DO/l). In this eutrophic state, DO increased exponentially during the daytime hours and then decreased during the night. The daily measurement showed an increase in the average DO of 2.31 mg/l (standard deviation of 1.56 mg/l), with average CODinlet fluctuations of 18.79 mg/l (standard deviation of 13.56 mg/l) and average CODoutlet of 14.38 mg/l (standard deviation 2.94 mg/l). Due to additional DO concentration coming from eutrophication during daylight, it was not possible to make a precise assessment of the effectiveness of the MBG aerator.

Polymeric precipitation inhibitor differently affects cocrystal surface and bulk solution phase transformations

During the dissolution of cocrystal particles, solution-mediated phase transformation (SMPT) can occur either on the particle surface (PS-SMPT) or in the bulk phase solution (BP-SMPT). In this study, we compared the effect of various polymers on PS-SMPT and BP-SMPT for the first time using carbamazepine saccharine cocrystal (CBZ-SAC) as a model drug. Polyethylene glycol 6000 (PEG), polyvinylpyrrolidone K-30 (PVP), hydroxypropyl methylcellulose (HPMC), hydroxypropyl methylcellulose acetate succinate (HPMC-AS), amino methacrylate copolymer (EPO), and methacrylic acid copolymers (L100-55) were used as polymeric precipitation inhibitors. In the non-sink dissolution test, CBZ-SAC rapidly transforms to CBZ dihydrate (CBZ DH) via PS-SMPT in the absence of polymers. The polymers enhanced the dissolution rate and subsequent supersaturated CBZ concentration in the order of HPMC-AS > HPMC > EPO ≫ PVP ≈ L100-55 ≈ PEG. On the other hand, in the solvent-shift precipitation test, these polymers inhibited the precipitation of CBZ DH in a different order (EPO > HPMC > HPMC-AS ≫ L100-55 ≈ PVP ≫ PEG). The polymers affected the crystal habit of CBZ DH differently between PS-SMPT and BP-SMPT. Direct PS-SMPT observation by real-time polarized light microscopy (RT-PLM) showed that PS-SMPT was significantly inhibited by HPMC-AS, HPMC, and EPO, but less by PVP, L100-55, and PEG. Differences in solid surface pH and heterogeneous nucleation were discussed as the reason for the difference in the inhibitory effect between polymers in PS-SMPT and BP-SMPT. In conclusion, the inhibitory effect of polymers can differ between PS-SMPT and BP-SMPT. For the successful development of a cocrystal formulation, it is important to select a potent inhibitor of PS-SMPT.

Understanding Symmetry Breaking at the Single-Particle Level via the Growth of Tetrahedron-Shaped Nanocrystals from Higher-Symmetry Precursors.

The vast majority of single crystalline metal nanoparticles adopt shapes in the Oh point group as a consequence of the symmetry of the underlying face-centered cubic (FCC) crystal lattice. Tetrahedra are a notable exception to this rule, and although they have been observed in several syntheses, their growth mechanism, and the symmetry-reduction process that necessarily characterizes it, is poorly understood. Here, a symmetry breaking mechanism is revealed by in situ liquid flow cell transmission electron microscopy (TEM) observation of seeded growth in which tetrahedra nanoparticles are formed from higher symmetry seeds. Real-time observation of the growth demonstrates a kinetically driven pathway during which rhombic dodecahedra nanoparticles transition to tetrahedra through tristetrahedra intermediates, with an accompanying surface facet evolution from {110} to {111} via {hhl} (where h > l), respectively. On the basis of these data, we propose a mechanism that relies on a rapid loss of inversion symmetry in the initial stages of the reaction, followed by differential reactivity of tips vs faces under conditions of relatively high supersaturation and moderate ligand concentration. The application of these insights to ex situ synthesis conditions allowed for an improved yield of tetrahedra nanoparticles. This work sheds an important mechanistic light on the crystallographic underpinnings of nanoparticle shape and symmetry transformations and highlights the importance of single-particle characterization tools for monitoring nanoscale phenomena.