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We developed a mass spectrometric soil-gas flux measurement system using a portable high-resolution multi-turn time-of-flight mass spectrometer, called MULTUM, and we combined it with an automated soil-gas flux chamber for the continuous field measurement of multiple gas concentrations with a high temporal resolution. The developed system continuously measures the concentrations of four different atmospheric gases (NO2, CH4, CO2, and field soil–atmosphere flux measurements of greenhouse gases (NO2, O2) ranging over 6 orders of magnitude at one time using a single gas sample. The measurements are performed every 2.5 min with an analytical precision (2 standard deviations) of ±34 ppbv for NO2; ±170 ppbv, CH4; ±16 ppmv, CO2; and ±0.60 vol %, O2 at their atmospheric concentrations. The developed system was used for the continuous field soil–atmosphere flux measurements of greenhouse gases (NO2, CH4, and CO2) and O2 with a 1 h resolution. The minimum quantitative fluxes (2 standard deviations) were estimated via a simulation as 70.2 µgNm-2h-1 for NO2; 139 µgCm-2h-1, CH4; 11.7 mg C m−2 h−1, CO2; and 9.8 g O2 m−2 h−1, O2. The estimated minimum detectable fluxes (2 standard deviations) were 17.2 µgNm-2h-1 for NO2; 35.4 µgCm-2h-1, CH4; 2.6 mg C m−2 h−1, CO2; and 2.9 g O2 m−2 h−1, O2. The developed system was deployed at the university farm of the Ehime University (Matsuyama, Ehime, Japan) for a field observation over 5 d. An abrupt increase in NO2 flux from 70 to 682 µgNm-2h-1 was observed a few hours after the first rainfall, whereas no obvious increase was observed in CO2 flux. No abrupt NO2 flux change was observed in succeeding rainfall events, and the observed temporal responses at the first rainfall were different from those observed in a laboratory experiment. The observed differences in temporal flux variation for each gas component show that gas production processes and their responses for each gas component in the soil are different. The results of this study indicate that continuous multiple gas concentration and flux measurements can be employed as a powerful tool for tracking and understanding underlying biological and physicochemical processes in the soil by measuring more tracer gases such as volatile organic carbon, reactive nitrogen, and noble gases, and by exploiting the broad versatility of mass spectrometry in detecting a broad range of gas species.

Severe winter haze accompanied by high concentrations of fine particulate matter (PM2.5) occurs frequently in the North China Plain and threatens public health. Organic matter (OM) and sulfate are recognized as major components of PM2.5, while atmospheric models often fail to predict their high concentrations during severe winter haze due to incomplete understanding of secondary aerosol formation mechanisms. By using a novel combination of single-particle mass spectrometry and an optimized ion chromatography method, here we show that hydroxymethanesulfonate (HMS), formed by the reaction between formaldehyde (HCHO) and dissolved SO2 in aerosol water, is ubiquitous in Beijing during winter. The HMS concentration and the molar ratio of HMS to sulfate increased with the deterioration of winter haze. High concentrations of precursors (SO2 and HCHO) coupled with low oxidant levels, low temperature, high relative humidity, and moderately acidic pH facilitate the heterogeneous formation of HMS, which could account for up to 15 % of OM in winter haze and lead to up to 36 % overestimates of sulfate when using traditional ion chromatography. Despite the clean air actions having substantially reduced SO2 emissions, the HMS concentration and molar ratio of HMS to sulfate during severe winter haze increased from 2015 to 2016 with the growth in HCHO concentration. Our findings illustrate the significant contribution of heterogeneous HMS chemistry to severe winter haze in Beijing, which helps to improve the prediction of OM and sulfate and suggests that the reduction in HCHO can help to mitigate haze pollution.

Purpose: To assess the image quality of a modified Fast three-dimensional (Fast 3D) mode wheel with sequential data filling (mFast 3D wheel) combined with a deep learning denoising technique (Advanced Intelligent Clear-IQ Engine [AiCE]) in contrast-enhanced (CE) 3D dynamic magnetic resonance (MR) imaging of the abdomen during a single breath hold (BH) by intra-individual comparison with compressed sensing (CS) with AiCE., Methods: Forty-two patients who underwent multiphasic CE dynamic MRI obtained with both mFast 3D wheel using AiCE and CS using AiCE in the same patient were retrospectively included. The conspicuity, artifacts, image quality, signal intensity ratio (SIR), signal-to-noise ratio (SNR), contrast ratio (CR), and contrast enhancement ratio (CER) of the organs were compared between these 2 sequences., Results: Conspicuity, artifacts, and overall image quality were significantly better in the mFast 3D wheel using AiCE than in the CS with AiCE (all p < 0.001). The SNR of the liver in CS with AiCE was significantly better than that in the mFast 3D wheel using AiCE (p < 0.01). There were no significant differences in the SIR, CR, and CER between the two sequences., Conclusion: A mFast 3D wheel using AiCE as a deep learning denoising technique improved the conspicuity of abdominal organs and intrahepatic structures and the overall image quality with sufficient contrast enhancement effects, making it feasible for BH 3D CE dynamic MR imaging of the abdomen., (© 2024. The Author(s).)

Human ascariasis is a soil-transmitted helminthiasis and remains a neglected tropical disease. Ascaris suum has the potential to cause cross-infections between humans and pigs. In this study, we present a rare case of a patient with asymptomatic infection by Ascaris suum. A 66-year-old male underwent colonoscopy, and a white linear worm body was found in the hepatic curvature. The worm was collected by aspiration and submitted to the laboratory for parasite identification. The patient had no symptoms related to parasitic infection. The worm was highly suspected to be of the genus Ascaris. Because of the difficulty of morphological classification, genetic analysis was performed. From PCR-restriction fragment length polymorphism results and sequence analysis of the internal transcribed spacer-1 region, it was determined to be A. suum. The experience with rapid differentiation of A. suum by performing genetic analysis will be useful for future examinations of parasitic infections., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Inc.)

For applying highly sensitive mass spectrometry to chemical analysis of aqueous samples, we have developed a novel technique using a new form of liquid droplets, which we call "aeromicelle" (AM), to deliver aqueous sample solutions directly into the vacuum region of a single-particle mass spectrometer in liquid form and conduct immediate mass analysis. AMs are generated by spraying an aqueous solution containing a surfactant at a concentration significantly lower than its critical micelle concentration (CMC). When the solution is sprayed, liquid droplets containing the surfactant are formed, which gradually dry in an air flow. Upon drying, the surfactant concentration in the droplet exceeds its CMC, and consequently, the surfactant molecules begin to cover the droplet surface. Finally, the surface is expected to be fully covered with surfactant molecules such as reverse micelles. The surface coverage helps suppress the evaporation of water, thereby enhancing the residence time of the liquid droplet. Our experimental results show that the AMs retained a liquid form for at least 100 s in air and survived even under vacuum conditions for further mass analysis: each AM delivered in the vacuum region of a single-particle mass spectrometer is ablated with an intense laser pulse and then, mass analyzed. Individual AMs generated from an aqueous solution containing CsCl were analyzed using a single-particle mass spectrometer. The Cs + ion peak was observed even in AMs generated from the 10 nM solution. The number of Cs atoms in each AM was estimated to be approximately 7 × 10 3 , which corresponds to 1.2 × 10 -20  mol (12 zmol). Meanwhile, in the mass analysis of tyrosine, both positive and negative fragmentation ions from tyrosine in AMs were observed in the mass spectrum and 4.6 × 10 5 (760 zmol) tyrosine molecules were detected., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Hiroshi Furutani, Michisato Toyoda reports financial support was provided by Japan Society for the Promotion of Science. Michisato Toyoda, Hiroshi Furutani, Takashi Kimoto reports financial support was provided by Japan Science and Technology Agency. Takashi Kimoto, Hiroshi Furutani, Michisato Toyoda has patent #JP6806795 issued to Kimoto Electric Co. LTD, Osaka University. Takashi Kimoto, Hiroshi Furutani, Michisato Toyoda has patent #US Patent App. 16/096,096 issued to Kimoto Electric Co. LTD, Osaka University., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Magnetosome-producing microorganisms can sense and move toward the redox gradient and have been extensively studied in terrestrial and shallow marine sediment environments. However, given the difficulty of sampling, magnetotactic bacteria (MTB) are poorly explored in deep-sea hydrothermal fields. In this study, a deep-sea hydrothermal vent chimney from the Southern Mariana Trough was collected using a remotely operated submersible. The mineralogical and geochemical characterization of the vent chimney sample showed an internal iron redox gradient. Additionally, the electron microscopy of particles collected by magnetic separation from the chimney sample revealed MTB cells with bullet-shaped magnetosomes, and there were minor occurrences of cuboctahedral and hexagonal prismatic magnetosomes. Genome-resolved metagenomic analysis was performed to identify microorganisms that formed magnetosomes. A metagenome-assembled genome (MAG) affiliated with Nitrospinae had magnetosome genes such as mamA, mamI, mamM, mamP , and mamQ . Furthermore, a diagnostic feature of MTB genomes, such as magnetosome gene clusters (MGCs), including mamA, mamP , and mamQ , was also confirmed in the Nitrospinae -affiliated MAG. Two lines of evidence support the occurrence of MTB in a deep-sea, inactive hydrothermal vent environment., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Nakano, Furutani, Kato, Kouduka, Yamazaki and Suzuki.)

Organic aerosols (OA) are major components of fine particulate matter, yet their formation mechanism remains unclear, especially in polluted environments. In this study, we investigated the diurnal chemical compositions and formation processes of OA in carbonaceous particles during winter in Beijing using aerosol time-of-flight mass spectrometry. We found that 84.5% of the measured carbonaceous particles underwent aging processes, characterized by larger diameter and more secondary species compared to fresh carbonaceous particles, and presented different chemical compositions of OA in the daytime and nighttime. During the day, under high O 3 concentrations, organosulfates and oligomers existed in the aged carbonaceous particles, which were mixed with a higher signal of nitrate compared with sulfate. At night, under high relative humidity, distinct spectral signatures of hydroxymethanesulfonate and organic nitrogen compounds, and minor signals of other hydroxyalkylsulfonates and high molecular weight organic compounds were present in the aged carbonaceous particles, which were mixed with a higher signal of sulfate compared with nitrate. Our results indicated that photochemistry contributed to OA formation in the daytime, while aqueous chemistry played an important role in OA formation in the nighttime. The findings can help improve the performance of air quality and climate models on OA simulation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The application of proton transfer ionization reaction mass spectrometry (PTR MS) combined with microscale supercritical fluid extraction (SFE) and supercritical fluid chromatography (SFC) aiming to quantitate single-cell fatty acid analysis levels was investigated. Using a microscale extraction vessel, the obtained low limits of quantitation (LLOQs) of arachidonic acid and arachidic acid were 1.2 and 2.7 fmol, respectively, by using less than 1 µL of sample on stainless steel frit. A series of phthalate, vitamin K 1 , and α-tocopherol were also tested, and the LLOQ was less than one femtomole for phthalate and 35 and 13 fmol for vitamin K 1 and α-tocopherol, respectively. A microliter portion of SFE extracts was introduced into the SFC column by split injection, improving the reproducibility of the chromatography and separation efficiency. The method in the present study has great potential to quantitate lipophilic molecules on the nanogram scale of a sample without complex preparation procedures., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Chemosynthetic organisms flourish around deep-sea hydrothermal vents where energy-rich fluids are emitted from metal sulfide chimneys. However, microbial life hosted in mineral assemblages in extinct chimneys lacking fluid venting remains largely unknown. The interior of extinct chimneys remains anoxic where the percolation of oxygenated seawater is limited within tightly packed metal sulfide grains. Given the scarcity of photosynthetic organics in deep seawater, anaerobic microbes might inhabit the grain boundaries energetically depending on substrates derived from rock-water interactions. In this study, we reported ultra-small cells directly visualized in grain boundaries of CuFeS 2 inside an extinct metal sulfide chimney from the southern Mariana Trough. Nanoscale solid analyses reveal that ultra-small cells are coated with Cu 2 O nanocrystals in grain boundaries enriched with C, N, and P. In situ spectroscopic and spectrometric characterizations demonstrate the distribution of organics with amide groups and a large molecular organic compound in the grain boundaries. We inferred that the ultra-small cells are anaerobes because of the fast dissolution of Cu 2 O nanocrystals in oxygenated solution. This Cu 2 O property also excludes the possibility of microbial contamination from ambient seawater during sampling. It is shown by 16S rRNA gene sequence analysis that the chimney interior is dominated by Pacearchaeota known to have anaerobic metabolisms and ultra-small cells. Our results support the potential existence of photosynthesis-independent microbial ecosystems in grain boundaries in submarine metal sulfides deposits on the early Earth., Competing Interests: KN and TY were employed by Shimadzu Corporation. YK was employed by TOYO Corporation. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Takamiya, Kouduka, Furutani, Mukai, Nakagawa, Yamamoto, Kato, Kodama, Tomioka, Ito and Suzuki.)

Proton-transfer-reaction (PTR) mass spectrometry (MS), a widely used method for detecting trace-levels of volatile organic compounds in gaseous samples, can also be used for the analysis of small non-volatile molecules by using supercritical fluid as a transporter for the molecules. Supercritical fluid extraction (SFE) is a method that permits lipophilic compounds to be rapidly and selectively extracted from complex matrices. The combination of the high sensitivity of PTR MS with the SFE is a potentially novel method for analyzing small molecules in a single cell, particularly for the analysis of lipophilic compounds. We preliminarily evaluated this method for analyzing the components of a single HeLa cell that is fixed on a stainless steel frit and is then directly introduces the SFE extracts into the PTR MS. A total of 200/91 ions were observed in positive/negative ion mode time-of-flight mass spectra, and the masses of 11/10 ions could be matched to chemical formulae obtained from the LipidMaps lipids structure database. Using various authentic lipophilic samples, the method could be used to detect free fatty acids in the sub-femtomole to femtomole order in the negative ion mode, the femtomole to sub-picomole order for fat-soluble vitamins, and the picomole order for poly aromatic hydrocarbons in both the positive and negative ion mode., (Copyright © 2022 Toshinobu Hondo, Chihiro Ota, Kohta Nakatani, Yumi Miyake, Hiroshi Furutani, Takeshi Bamba, and Michisato Toyoda.)

We have developed a rapid and sensitive analytical method for α-tocopherol and its oxidative products by combining online hyphenation of supercritical fluid extraction-supercritical fluid chromatography (SFC) with proton transfer reaction (PTR) ionization mass spectrometry (MS). α-Tocopherol is a well-known antioxidant that plays a vital role in the antioxidant defense system in plant cells. However, studies on the cellular mechanisms of α-tocopherol have been limited owing to the lack of a rapid analytical method, which limits the comparison of plant cells incubated in various conditions. Additionally, complex sample preparation and long chromatography separation times are required. Moreover, the majority of the involved molecules are a combination of isomers, which must be separated before applying tandem MS. α-Tocopherol produces the α-tocopheroxyl radical in the first step of its antioxidant function; another ion with the same mass may also be generated from the source. SFC separation effectively distinguished the observed ions from their oxidative products in the sample and those produced during the ionization reaction process. This method enabled the measurement of α-tocopherol and its oxidative products such as α-tocopheroxyl radical and α-tocopheryl quinone in approximately 3 min per sample, including the time required for sample preparation., (Copyright © 2022 Chihiro Ota, Toshinobu Hondo, Yumi Miyake, Hiroshi Furutani, and Michisato Toyoda.)

Proton-transfer-reaction (PTR) mass spectrometry (MS) is capable of detecting trace-level volatile organic compounds (VOCs) in gaseous samples in real time. Therefore, PTR-MS has become a popular method in many different study areas. Most of the currently reported PTR-MS applications are designed to determine volatile compounds. However, the method might be applicable for nonvolatile organic compound detection. Supercritical fluid chromatography (SFC) has been studied in the last 5 decades. This approach has high separation efficiency and predictable retention behavior, making separation optimization easy. Atmospheric ionization techniques, such as atmospheric chemical ionization (APCI) and electrospray ionization (ESI), are the most studied SFC-MS interfaces. These processes require the addition of makeup solvents to prevent precipitation or crystallization of the solute while depressurizing the mobile phase. In contrast, the PTR process is carried out in a vacuum; supercritical carbon dioxide may release solute into the PTR flow tube without a phase transition as long as it is maintained above a critical temperature. Therefore, this might constitute yet another use for the SFC-MS interface. Caffeine and a few other nonpolar compounds in supercritical carbon dioxide were successfully detected with time-of-flight MS without adding solvent by using preliminarily assembled supercritical flow injection and supercritical fluid extraction (SFE)-PTR interfaces.

A new family of liquid π-donors, lipophilic dihydrophenazine (DHP) derivatives, show remarkably high π-electron-donor property which exhibit supramolecular alternating copolymerization with 7,7,8,8-tetracyanoquinodimethane (TCNQ), giving ionic charge-transfer (ICT) complexes. The ICT complexes form distinct columnar liquid crystalline (LC) mesophases with well-defined alternating molecular alignment as demonstrated by UV-Vis-NIR spectra, IR spectra, and X-ray diffraction (XRD) patterns. These liquid crystalline ICT complexes display unique phase transitions in response to mechanical stress: the columnar ICT phase is converted to macroscopically oriented smectic-like mesophases upon applying shear force. Although there exist reports on the formation of ICT in the crystalline state, this study provides the first rational identification of ICT mesophases based on the spectroscopic and structural data. The liquid crystalline ICT phases are generated by strong electronic interactions between the liquid π-donors and solid acceptors. It clearly shows the significance of simultaneous fulfillment of strong π-donating ability and ordered self-assembly of the stable ICT pairs. The flexible, stimuli-responsive structural transformation of the ICT complexes offer a new perspective for designing processable CT systems with controlled hierarchical self-assembly and electronic structures., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Iguchi, Furutani and Kimizuka.)

High molecular weight organic compounds (HMW-OCs), formed as secondary organic aerosols (SOA), have been reported in many laboratory studies. However, little evidence of HMW-OCs formation, in particular during winter season in the real atmosphere, has been reported. In January 2013, Beijing faced historically severe haze pollution, in which the hourly PM 2.5 concentration reached as high as 974 μg m -3 . Four typical haze events (HE1 to HE4) were identified, and HE2 (Jan. 9-16) was the most serious of these. Based on the hourly observed chemical composition of PM 2.5 and the daily organic composition analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS), we found that abundant ion peaks in m/z 200-850 appeared on heavy haze days, whereas these were negligible on a clear day, indicating the existence of HMW-OCs in the wintertime haze. A negative nonlinear correlation between HMW-OCs and O 3 suggested that gas oxidation was not likely to be the dominant mechanism for HMW-OCs formation. During the heavy haze events, the relative humidity and mass ratio of H 2 O/PM 2.5 reached as high as 80% and 0.2, respectively. The high water content and its good positive correlation with HMW-OCs indicated that an aqueous-phase process may be a significant pathway in wintertime. The evidence that acidity was much higher during HE2 (0.37 μg m -3 ) than on other days, as well as its strong correlation with HMW-OCs, indicated that acid-catalyzed reactions likely resulted in HMW-OCs formation during the heavy winter haze in Beijing., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The influence of oceanic biological activity on sea spray aerosol composition, clouds, and climate remains poorly understood. The emission of organic material and gaseous dimethyl sulfide (DMS) from the ocean represents well-documented biogenic processes that influence particle chemistry in marine environments. However, the direct emission of particle-phase biogenic sulfur from the ocean remains largely unexplored. Here we present measurements of ocean-derived particles containing reduced sulfur, detected as elemental sulfur ions (e.g., (32)S(+), (64)S2(+)), in seven different marine environments using real-time, single particle mass spectrometry; these particles have not been detected outside of the marine environment. These reduced sulfur compounds were associated with primary marine particle types and wind speeds typically between 5 and 10 m/s suggesting that these particles themselves are a primary emission. In studies with measurements of seawater properties, chlorophyll-a and atmospheric DMS concentrations were typically elevated in these same locations suggesting a biogenic source for these sulfur-containing particles. Interestingly, these sulfur-containing particles only appeared at night, likely due to rapid photochemical destruction during the daytime, and comprised up to ∼67% of the aerosol number fraction, particularly in the supermicrometer size range. These sulfur-containing particles were detected along the California coast, across the Pacific Ocean, and in the southern Indian Ocean suggesting that these particles represent a globally significant biogenic contribution to the marine aerosol burden.