Coalescence and mixing dynamics of droplets in acoustic levitation by selective colour imaging and measurement.

Acoustic levitation is well-suited to 'lab-on-a-drop' contactless chemical analysis of droplets. Rapid mixing is of fundamental importance in lab-on-a-drop platforms and many other applications involving droplet manipulation. Small droplets, however, have low Reynolds numbers; thus, mixing via turbulence is not possible. Inducing surface oscillation is effective in this regard, however, the relationship between internal flow and mixing dynamics of droplets remains unclear. In this study, we conducted a set of simultaneous optical measurements to assess both the flow field and the distribution of fluid components within acoustically levitated droplets. To achieve this, we developed a technique to selectively separate fluorescent particles within each fluid, permitting the measurement of the concentration field based on the data from the discrete particle distribution. This approach revealed a relationship between the mixing process and the internal flow caused by surface oscillation. Thus, the internal flow induced by surface oscillation could enhance droplet mixing. Our findings will be conducive to the application and further development of lab-on-a-drop devices.

[Plasticizers Used in Polyvinyl Chloride Toys (2019-2020)].

We determined the fifteen types of plasticizers, including four kinds of phthalic acid esters (PAEs) used in 220 polyvinyl chloride (PVC) toys on Japanese market from 2019 to 2020. Three kinds of previously undetected types of PAEs were also detected, but not identified in this study. Di (2-ethylhexyl) terephthalate (DEHTP) was the highest detection rate in 209 soft PVC toys out of 220 toys, with 71.2% for designated toys and 88.9% for not-designated toys, respectively, showing a gradual increase from the previous reports in 2009 and 2014. On the other hand, the usages of o-acetyl tributyl citrate and adipic acid esters decreased, but the six types of PAEs prohibited to use for the designated toys in Japan were not detected in them, the usage of diisobutyl phthalate were increased. In contrast, four types of PAEs were detected in not-designated toys. Among them, the detection ratio of di (2-ethyhexyl) phthalate decreased to about 1/10. The content levels of plasticizers in per each sample were continued to keep low level from the report five years ago. These results showed that the main plasticizer used in PVC toys is DEHTP, and that the usage of other plasticizers was decreased.

[Inter-laboratory Study on the Modified Methods for Analyzing Bisphenol A Content for Migration Tests from Polycarbonate Food Apparatuses, Containers, and Packaging].

An inter-laboratory study involving 24 laboratories was conducted to validate the modified analytical method for the migration solution of heptane for the determination of bisphenol A migrating from polycarbonate food processing materials. In this study, two concentrations of samples were blindly coded. Each laboratory determined the analyte (bisphenol A, phenol and p-tert-butylphenol) concentration in each sample according to the established protocol. The obtained values were analyzed statistically using internationally accepted guidelines. Horwitz ratios were calculated based on the reproducibility relative standard deviation (RSDR), which was estimated from the inter-laboratory study, and predicted RSDR, which was calculated using the Horwitz/Thompson equation. Horwitz ratios of the two samples ranged from 0.15 to 0.37 for the three compounds, meeting the performance criteria of less than 2 set by the Codex Alimentarius for analytical method approval. These results showed that this modified analytical method shows good performance as an analytical method for the migration solution of heptane.

[Modified Methods for Analyzing Bisphenol A Content for Migration Tests from Polycarbonate Food Apparatuses, Containers, and Packaging].

A validation study was performed on the modified analytical method for the migration solution of heptane, 20% ethanol and 4% acetic acid for the determination of bisphenol A migrating from polycarbonate food apparatuses, containers, and packaging. The analytes for the method were bisphenol A, phenol and p-tert-butylphenol. The repeatability, within-laboratory reproducibility and trueness of the method was estimated in the range of 0.2-1.8%, 0.4-2.6% and 95-102% respectively. These results showed that the method is useful as an analytical method for the migration solution of heptane, 20% ethanol and 4% acetic acid. Furthermore, the applicability of the determination methods with a fluorescence detector was verified. As a result of the validation study, the repeatability, within-laboratory reproducibility and trueness of the method was estimated in the range of 0.1-2.9%, 0.2-3.1% and 94-101% respectively. It was confirmed that the measurement with a fluorescence detector is also available.

Determination of potential volatile compounds in polyethylene terephthalate (PET) bottles and their short- and long-term migration into food simulants and soft drink.

Head space (HS)-GC-MS was used to analyze possible migration of volatile compounds from polyethylene terephthalate (PET) bottles for soft drinks, and a total of six compounds were identified. Next, a rapid, simple, and accurate simultaneous method was established using purge-and-trap (PT)-GC-MS, to quantify their amounts in the liquid contents after short- and long-term storage in PET bottles. Starting with brand-new PET bottles, the maximum migration of 2-methyl-1,3-dioxolane into distilled water and 50 % aqueous ethanol after 2 years at 25 °C were 2.3 and 19 ng/mL, respectively. In commercially available bottled mineral water sold inside and outside Japan, we were able to detect 2-methyl-1,3-dioxolane in the same way. While nonanal was also detected in some products, 2-methyl-1,3-dioxolane was confirmed as the main volatile compound. Finally, the human exposure to 2-methyl-1,3-dioxolane was estimated based on the per capita intake of soft drinks in Japan and the migration amount in this study.

[Validation Study on Migration Test for Plastic Food Utensils, Containers, and Packaging].

Migration test of food utensils, containers, and packaging is an important test method for confirming the safety and their compliance to the standards. However, there is little report on inter-laboratory study which was performed to evaluate the entire migration test, including migration operations and quantification. An interlaboratory study was performed participating 22 laboratories using 8 types of model synthetic resin samples containing 10 substances with a wide range of Log Pow values to evaluate the accuracy of the entire migration test. As a result, most of HorRat (r) values met the target criteria (0.3

[Inter-laboratory Study on the Modified Method Assessment for the Determining Methanol Content in Kitchen Detergents].

We modified a method for determining methanol content in detergents used in kitchens. Furthermore, an inter-laboratory study was conducted in 10 laboratories to validate the modified method. In this study, two concentrations of samples were blindly coded. Each laboratory determined the methanol content in each sample according to a protocol. The determined values were statistically analyzed according to an international harmonized guideline. HorRat values were calculated based on the reproducibility relative standard deviation (RSDR) which was estimated from the interlaboratory study, and predicted RSDR calculated from the Horwitz/Thompson equation. The HorRat values of the two samples were 0.8 and 1.8, meeting the performance criteria of less than 2 set by the Codex Alimentarius for analytical method approval. These results confirm that this modified analytical method shows good performance as an analytical method for determining methanol content in kitchen detergents.

NaCl dependent production of coniferin in Alluaudiopsis marnieriana suspension cultured cells.

A stable salt-tolerant cell-suspension culture of Alluaudiopsis marnieriana was established, and intracellular compounds that accumulated under salt-stress conditions were investigated. HPLC/MS, and NMR analyses indicated that enhanced accumulation of coniferin was found during the growth phase in medium containing 150 mM NaCl. Coniferin or its derivatives may play an important role in salt-tolerance mechanisms in this plant.

Determination of formaldehyde and acetaldehyde levels in poly(ethylene terephthalate) (PET) bottled mineral water using a simple and rapid analytical method.

A simple and rapid analytical method was developed for the determination of formaldehyde (FA) and acetaldehyde (AA) contents in water. FA and AA were derivatized by 2,4-dinitrophenylhydrazine in an LC vial for 20 min at room temperature, about 25 °C, and analyzed using LC-MS/MS. The calibration curve exhibited excellent linearity for FA and AA concentrations of 2-150 ng/mL. Recovery tests using ultra-pure water and commercially available PET-bottled mineral water samples showed good trueness and precision. We determined the FA and AA contents in 105 PET-bottled mineral water samples on the Japanese market using this method. FA was detected in 61% of the samples at levels from 2.6 to 31.4 ng/mL, while AA was detected in 68% at levels from 5.3 to 143.5 ng/mL. These results demonstrate that the concentrations of FA and AA in PET-bottled mineral water on the Japanese market have not changed significantly over the last decade.

Diffusion enhancement in a levitated droplet via oscillatory deformation.

Recent experimental results indicate that mixing is enhanced by a reciprocal flow induced inside a levitated droplet with an oscillatory deformation [T. Watanabe et al., Sci. Rep. 8, 10221 (2018)2045-232210.1038/s41598-018-28451-5]. Generally, reciprocal flow cannot convect the solutes in time average, and agitation cannot take place. In the present paper, we focus on the diffusion process coupled with the reciprocal flow. We theoretically derive that the diffusion process can be enhanced by the reciprocal flow, and the results are confirmed via numerical calculation of the over-damped Langevin equation with a reciprocal flow.

Coalescence Dynamics of Acoustically Levitated Droplets.

The contactless coalescence of a droplet is of paramount importance for physical and industrial applications. This paper describes a coalescence method to be used mid-air via acoustic levitation using an ultrasonic phased array system. Acoustic levitation using ultrasonic phased arrays provides promising lab-on-a-drop applications, such as transportation, coalescence, mixing, separation, evaporation, and extraction in a continuous operation. The mechanism of droplet coalescence in mid-air may be better understood by experimentally and numerically exploring the droplet dynamics immediately before the coalescence. In this study, water droplets were experimentally levitated, transported, and coalesced by controlled acoustic fields. We observed that the edges of droplets deformed and attracted each other immediately before the coalescence. Through image processing, the radii of curvature of the droplets were quantified and the pressure difference between the inside and outside a droplet was simulated to obtain the pressure and velocity information on the droplet's surface. The results revealed that the sound pressure acting on the droplet clearly decreased before the impact of the droplets. This pressure on the droplets was quantitatively analyzed from the experimental data. Our experimental and numerical results provide deeper physical insights into contactless droplet manipulation for futuristic lab-on-a-drop applications.

Rapid identification of polyamides using direct analysis in real time mass spectrometry.

RATIONALE: Polyamide (PA) is the generic name of polymers synthesized by linking monomers via amide bonds, and various types of PAs with different monomer compositions are known. Distinguishing PA polymers is useful in directing monomer residual testing, product testing, and reverse engineering, but is analytically challenging and cumbersome. To simplify this, we explored the applicability of direct analysis in real time mass spectrometry (DART-MS) for screening PA polymers. METHODS: A DART ion source coupled to a quadrupole Orbitrap (high-resolution (HR) mass spectrometer) was employed for this study. Ten types of PA polymers and four retail samples were evaluated. The DART-HRMS data for these samples, as well as the DART-MS/MS (MS2 ) data for PA6 and PA66, were obtained, and their repeatability was assessed across days/calibrations, operators, and equipments. RESULTS: Ions corresponding to the cyclic or linear monomers and oligomers of each PA polymer were detected in each DART-HR mass spectrum. Although similar DART-HR mass spectra were obtained for PA6, PA66, and PA6/PA66 (polymer blends of PA6 and PA66), their DART tandem mass spectra were completely different. The analysis was repeatable, and nearly identical DART tandem mass spectra were obtained on different days, by different operators, and with different equipment. This technique was successfully applied to commercially available samples. CONCLUSIONS: Ten types of PA polymers were distinguished using DART-HRMS and DART-MS2 , and their identification using these techniques was straightforward as the characteristic ions for each PA polymer were identified and detected. Furthermore, the spectra were obtained rapidly. Therefore, DART-HRMS can be considered an efficient screening technique for the rapid identification and differentiation of PA polymers.

Acoustic Manipulation of Droplets under Reduced Gravity.

Contactless manipulation of matter is essential for studying physical phenomena. Acoustic manipulation of liquid samples using ultrasonic phased arrays provides a novel and attractive solution for mid-air manipulation, such as levitation, transportation, coalescence, mixing, separation, evaporation, and extraction, with a simple and single sequence. Despite the importance of gravity in droplet dynamics, its effect on a levitated droplet with an ultrasonic phased array remains unclear. To disseminate acoustic manipulation, better understanding of the fundamental physics of a droplet manipulated by ultrasonic phased arrays is required. Here, we show contactless levitation, transportation, and coalescence of multiple droplets under both ground and reduced gravity. Under ground gravity, the possible levitation size of the sample is limited to below the half wavelength of sound. Under reduced gravity, however, droplets that are larger than the limit can be successfully levitated, transported, and coalesced. Furthermore, the threshold of sound pressure for droplet levitation and manipulation could be minimised with the suppression of nonlinear acoustic phenomena under reduced gravity. These insights promote the development of contactless manipulation techniques of droplets for future space experiment and inhabitancy.

[Headspace GC/MS Analysis of Residual Solvents in Laminated Films Used for Food Packaging].

Multilayer laminated films may contain organic solvents derived from adhesives, printing inks and so on. A headspace-GC/MS analysis method for the simultaneous determination of 30 substances such as toluene, xylene, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, methanol, ethanol, was developed. A N,N-dimethyl formamide solution containing an internal standard substance was added to the sample. After leaving overnight at room temperature, the headspace gas was analyzed by GC/MS. This method was applicable to a laminate film made of various materials. The organic solvents such as toluene, ethyl acetate, and heptane were detected from 6 out of 42 food packaging bags made from laminated film on Japanese market using this method.

[Changes in Status of Plasticizers Used in Polyvinyl Chloride Toys].

Analytical survey of plasticizers used in about 500 polyvinyl chloride (PVC) toys in Japanese market was performed in 2014. The results obtained were compared with those obtained in 2009. Fifteen types of plasticizers including di (2-ethylhexyl) terephthalate (DEHTP) were detected. These plasticizers were also detected in the products in 2009, suggesting that the types of plasticizers used in PVC toys have not been changed. Among these detected plasticizers, the detection ratios of DEHTP were 60.3 and 73.7% in both designated and not-designated toys, respectively, both of which are the highest. These ratios are over 20-points higher than those in 2009. The six types of phthalic acid esters (PAEs) prohibited to use for the designated toys in Japan were not detected in designated toys used in this study. However, four types of PAEs, including three types of prohibited PAEs, were detected in not-designated toys with the detection ratios from 2.8 to 15.5%. These ratios are lower than those in 2009. The content levels of plasticizers used in the toys are lower than those in 2009. These results show that the main plasticizer used in PVC toys is DEHTP, and that the usage levels of plasticizers have been decreased.

Six-year monitoring study of 137Cs discharge from headwater catchments after the Fukushima Dai-ichi Nuclear Power Plant accident.

Since headwater catchments are the source areas of 137Cs for downstream river systems, 137Cs discharge from headwater areas needs to be evaluated. Dissolved form (Dissolved), coarse organic matter (Org), and suspended sediments (SS) were sampled and 137Cs concentrations were measured from June 2011 to November 2016 in four headwater catchments in Yamakiya District, located 35 km northwest of the Fukushima Dai-ichi Nuclear Power Plant (FDNPP). The data up to September 2013 (2.5 y after the accident) have been already published (Iwagami et al., 2017a, b). The data up to November 2016 (5.7 y after the accident) are newly reported in the present paper together with data at a new sampling site. The whole data from June 2011 to November 2016 is discussed. The normalized 137Cs concentrations (137Cs concentrations normalized by the average deposition density of each catchment) in Dissolved, Org, and SS were in the order of 10-6 m2/L, 10-2 m2/kg, and 10-1 m2/kg, respectively, before 2013 and declined to around 10-8 m2/L, 10-4 m2/kg, and 10-2 m2/kg, respectively, in 2016. As a result of the decontamination program, the discharge of SS increased, whereas 137Cs concentrations in SS declined significantly and the total flux of 137Cs decreased. Although the clear effect of land use on decline trend in normalized 137Cs concentrations in Dissolved was not found, more data are necessary for elucidating the relation between them.

Groundwater age and mixing process for evaluation of radionuclide impact on water resources following the Fukushima Dai-ichi nuclear power plant accident.

Radionuclide contamination of groundwater causes critical impacts on water resources, human lives, and ecosystems. The intrusion of radionuclides into the groundwater flow system in Fukushima, Japan, could be illuminated by determining groundwater age and mixing processes. To do this, periodical field surveys were conducted in catchments contaminated by the Fukushima Dai-ichi Nuclear Power Plant accident. Sampling began in May 2011, which was 2 months after the disaster, and continued through June 2012. Chlorofluorocarbon (CFCs), tritium, and oxygen and hydrogen stable isotopes were used as environmental tracers. The observed tritium concentrations suggested that the water contained accident-derived radionuclides that exceeded the natural background baseline. Groundwater ages in the selected two headwater catchments were estimated to be between 10 and 26 years by combined use of multiple CFCs concentrations. In addition, the governing groundwater flow system was mostly approximated by a piston flow model; however, modern water fraction was also suggested based on the relationship between CFC-11 and CFC-12. The estimated water age and isotopic signals among stream water, spring water, and groundwater revealed that the intrusion of radionuclides into the groundwater was caused by the mixing between groundwater and modern water sources such as soil water and precipitation with relatively high radionuclide concentrations. This mixing was facilitated by a weathered and fractured granite bedrock and a thin unsaturated subsurface layer in the study area. Continued long-term monitoring of radionuclides in the groundwater will be necessary for water resources management in the future. CAPSULE: Radionuclide intrusion into the groundwater is related to the mixing between radionuclide-poor groundwater and modern water with relatively high radionuclide concentration.

[A Case of Diffuse Large B-Cell Lymphoma of the Ascending Colon].

A 72-year-old man presented with right lower abdominal pain. Abdominal enhanced CT showed a large tumor in the ascending colon. Colonoscopyrevealed a type 2 tumor infiltrating three-quarters of the ascending colon. The biopsyspecimen showed a malignant lymphoma. Thus, the patient underwent ileocecal resection with D3 lymph node dissection. The histopathological diagnosis was primarydiffuse large B-cell lymphoma of the ascending colon. Post-operative PET-CT showed disseminated extra-nodal involvement, Stage Ⅳ(Lugano staging system). He was administered 2 courses of rituximab plus cyclophosphamide, doxorubicin, vincristine, and prednisolone chemotherapy. However, the patient was diagnosed with progressive disease. He received several chemotherapies and finallydied 8 months after surgery. We report our present case and literature review.

Micellar Effects on the Hydrolysis Reaction of an Anionic Surfactant in Aqueous Solution.

The hydrolysis mechanisms of 2-sulfoalkanoic acid methyl ester salts (methyl ester sulfonate, MES) were studied. Under acidic, neutral, and alkaline conditions, the hydrolysis rates of MES were strongly affected by the state of aggregation and the hydrolysis rate changed at the critical micelle concentration (CMC). Under acidic conditions, the hydrolysis rates of MES were enhanced by micellar formation and correlated quantitatively with the amount of protons bound on the micellar surfaces being measured by the electric conductivity along with fluorescence and hydrogen-ion electrode measurements. MES having longer acyl chain lengths showed higher hydrolysis rates above the CMC because of the many bound protons and the higher degree of counterion binding to the micelle, ß. The rates were affected by the type of counterion and followed the order of sodium > potassium > calcium salts of MES. In alkaline conditions, the rates of MES hydrolysis were suppressed to lower values by micelle formation and MES with longer acyl chain lengths showed lower rates above the CMC. Additionally, the hydrolysis rates of MES under neutral conditions were suppressed to a very low value by micelle formation. These mechanisms of inhibitory effect of hydrolysis by the aggregation should be dominated by the electrical repulsive interactions between hydroxyl anions and anionic micellar surfaces, as well as by interference with the penetration of the hydroxyl anion to the ester group in the micelles for alkaline hydrolysis and by interference from water molecules for neutral hydrolysis.

[Establishment of Test Methods for Overall Migration Test into Vegetable Oil Applied to Food Contact Materials Intended for Contact with Oils and Fatty Foods].

The evaporation residue test designated in the Japanese Food Sanitation Act is used to determine the total migration amount of substances that food contact materials release into foods. Vegetable oil would be the most suitable food simulant for oils and fatty foods, but it is difficult to remove by heating due to its high boiling point, so heptane and 20％ ethanol are used as substitute food simulants in the test for plastics and rubbers. The EU has introduced an overall migration test into olive oil for plastics intended to come into contact with oils and fatty foods. This test method is described in European Standard EN1186-2. However, this method has several problems. Therefore, we improved the procedures for weighing samples in a desiccator containing 43％ sulfuric acid, extraction of the absorbed vegetable oil using the soaking method with an internal standard, methyl esterification of vegetable oil using sodium methoxide, and the GC conditions for the determination of vegetable oil. The improved method is simpler and much quicker than the original method, and the harmfulness of the reagents is reduced. It can be applied to both plastics and rubbers. Comparative trials showed that the results obtained with this method and EN1186-2 method are equivalent.