Aerosol emissions and gravity waves of Taal volcano.

The Taal volcano (14.0 N, 121.0 E) in Philippines erupted in January-February 2020, with a part of aerosols drifted northward and detected by a lidar system at Kaohsiung city (22.37 N, 120.15 E), Taiwan. The aerosol observed on Feb 11 is special for its high-altitude distributions at 4-7 km with discrete structures which can be resolved into a sinusoidal oscillation of ~ 30 min period, suggesting a case of wave event caused by the eruptions. We report in this paper the gravity wave generated by the volcanic eruptions and its effects on aerosol emissions. By studying the temperature and pressure data in the Taal region using radiosonde data, we found atmospheric gravity waves with powers correlated with the optical thickness (AOD) at 550 nm measured by the Moderate Resolution Imaging Spectrometer (MODIS) satellite. This study presents the first observation of modulation of the aerosol emissions by the volcanic gravity waves and a case of coupling of dynamics and chemistry.

Optical properties of volcanic aerosols from eruptions of Nishinoshima Island observed in Southern Taiwan.

In July-August 2020, the volcano on Nishinoshima Island erupted with a moderate scale. The emitted aerosols arrived in Taiwan in early August and caused hazy air conditions in a few cities. In the city of Kaohsiung (KS) in southern Taiwan, the volcanic aerosols were observed with a combination of the aerosol robotic network (AERONET), several ground monitoring stations, and a lidar system. Increasing aerosol loadings were observed, beginning on 5 August 2020, based on a ground PM10/PM2.5 and the aerosol optical depth (AOD) of AERONET. Lidar measurements showed strong aerosol layers at heights of 0-2 km comparable to AERONET AOD. Optical properties including AOD, Angström exponent (AE), lidar backscattering coefficient, and depolarization ratio are measured with the source investigated using the back and forward trajectory studies.

Micro-droplet Trapping and Manipulation: Understanding Aerosol Better for a Healthier Environment.

Understanding the physicochemical properties and heterogeneous processes of aerosols is key not only to elucidate the impacts of aerosols on the atmosphere and humans but also to exploit their further applications, especially for a healthier environment. Experiments that allow for spatially control of single aerosol particles and investigations on the fundamental properties and heterogeneous chemistry at the single-particle level have flourished during the last few decades, and significant breakthroughs in recent years promise better control and novel applications aimed at resolving key issues in aerosol science. Here we propose graphene oxide (GO) aerosols as prototype aerosols containing polycyclic aromatic hydrocarbons, and GO can behave as two-dimensional surfactants which could modify the interfacial properties of aerosols. We describe the techniques of trapping single particles and furthermore the current status of the optical spectroscopy and chemistry of GO. The current applications of these single-particle trapping techniques are summarized and interesting future applications of GO aerosols are discussed.

Ionic-strength and pH dependent reactivities of ascorbic acid toward ozone in aqueous micro-droplets studied using aerosol optical tweezers.

The heterogeneous oxidation reaction of single aqueous ascorbic acid (AH2) aerosol particles with gas-phase ozone was investigated in this study utilizing aerosol optical tweezers with Raman spectroscopy. The measured liquid-phase bimolecular rate coefficients of the AH2 + O3 reaction exhibit a significant pH dependence, and the corresponding values at ionic strength 0.2 M are (3.1 ± 2.0) × 105 M-1 s-1 and (1.2 ± 0.6) × 107 M-1 s-1 for pH ≈ 2 and 6, respectively. These results measured in micron-sized droplets are in agreement with those from previous bulk measurements, indicating that the observed aerosol reaction kinetics can be solely explained by liquid phase diffusion and AH2 + O3 reaction. Furthermore, the results indicate that high ionic strengths could enhance the liquid-phase rate coefficients of the AH2 + O3 reaction. The results also exhibit a negative ozone pressure dependence that can be rationalized in terms of a Langmuir-Hinshelwood type mechanism for the heterogeneous oxidation of AH2 aerosol particles by gas-phase ozone. The results of the present work imply that in acidified airway-lining fluids the antioxidant ability of AH2 against atmospheric ozone will be significantly suppressed.

Giant Zeeman Splitting for Monolayer Nanosheets at Room Temperature.

Giant Zeeman splitting and zero-field splitting (ZFS) are observed in 2D nanosheets that have monolayers of atomic thickness. In this study, single-crystalline CdSe(ethylenediamine)0.5 and Mn2+-doped nanosheets are synthesized via a solvothermal process. Tunable amounts of Mn2+(0.5-8.0%) are introduced, resulting in lattice contraction as well as phosphorescence from five unpaired electrons. The exciton dynamics are dominated by spin-related electronic transitions (4T1 → 6A1) with long lifetimes (20.5, 132, and 295 µs). Temperature-varied EPR spectroscopy with spectral simulation reveals large ZFS (D = 3850 MHz) due to axial distortion of substituted Mn2+ (S = 5/2). In the magnetic circular dichroism (MCD) measurements, we observed giant Zeeman splitting with large effective g values (up to 231 ± 21), which implies huge sp-d exchange interactions in 2D monolayer regimes, leading to diluted magnetic semiconductor (DMS) materials.

Nitrogen-Doped Carbon Dots from Averrhoa carambola Fruit Extract as a Fluorescent Probe for Methyl Orange.

In this study, a simple and green hydrothermal treatment was performed to prepare nitrogen-doped carbon dots (NCDs) from Averrhoa carambola (AC) fruit extract as a carbon precursor and L-arginine (Arg) as a nitrogen dopant. The AC-NCDs were characterized by UV light, fluorescence spectroscopy, transmission electron microscopy, FTIR spectroscopy, Raman spectroscopy, UV-vis spectroscopy, and zeta potential analyzer. The AC-NCDs were spherical and the average diameter was estimated to be 6.67 nm. The AC-NCDs exhibited the maximum emission intensity at 446 nm with 360 nm excitation wavelength. The fluorescence quenching behavior of AC-NCDs after interacting with methyl orange (MO) dye was studied. The interaction of AC-NCDs and MO was achieved within 3 min and the fluorescence quenching was maintained to a fixed value even after 30 min. The linearity was obtained in the range of 1 to 25 µM MO with a 0.30 µM detection limit. Furthermore, the pH values affected the quenching behavior of the AC-NCDs/MO system where the interaction mechanisms were driven by the electrostatic interaction, π-π interaction, inner filter effect, and energy transfer. The pH 5 maintained higher quenching efficiency while other pH values slightly decreased the quenching efficiency. Incoming applications, the AC-NCDs can be used in various important fields, especially for environmental protection.

Cranberry Beans Derived Carbon Dots as a Potential Fluorescence Sensor for Selective Detection of Fe3+ Ions in Aqueous Solution.

Recently, synthesis, characterization, and application of carbon dots have received much attention. Natural products are the effectual carbon precursors to synthesize carbon dots with fascinating chemical and physical properties. In this study, the fluorescent sensor of carbon dots derived from cranberry beans without any functionalization and modification was developed. The carbon dots were prepared with a cheap, facile, and green carbon precursor through a hydrothermal treatment method. The synthetic process was toxic chemical-free, convenient, and environmentally friendly. To find the optimized synthetic conditions, the temperature, heating time duration, and carbon precursor weight were evaluated. The prepared carbon dots were characterized by UV light, transmission electron microscopy, Raman, Fourier transform infrared, UV-vis, and fluorescence spectroscopy. The resulting carbon dots exhibit stable fluorescence with a quantum yield of approximately 10.85%. The carbon dots emitted the broad fluorescence emission range between 410 and 540 nm by changing the excitation wavelength and were used for the detection of Fe3+ ions at the excitation of 380 nm. It is found that Fe3+ ions induced the fluorescence intensity quenching of the carbon dots stronger than other heavy metals and the Fe3+ ion detection can be achieved within 3 min. Spectroscopic data showed that the obtained carbon dots can detect Fe3+ ions within the wide concentration range of 30-600 µM with 9.55 µM detection limit.

Temperature-Dependent Rate Coefficient for the Reaction of CH3SH with the Simplest Criegee Intermediate.

The kinetics of the reaction of the simplest Criegee intermediate CH2OO with CH3SH was measured with transient IR absorption spectroscopy in a temperature-controlled flow reaction cell, and the bimolecular rate coefficients were measured from 278 to 349 K and at total pressure from 10 to 300 Torr. The measured bimolecular rate coefficient at 298 K and 300 Torr is (1.01 ± 0.17) × 10-12 cm3 s-1. The results exhibit a weak negative temperature dependence: the activation energy Ea ( k = Ae- Ea/ RT) is -1.83 ± 0.05 kcal mol-1, measured at 30 and 100 Torr. Quantum chemistry calculations of the reaction rate coefficient at the QCISD(T)/CBS//B3LYP/6-311+G(2d,2p) level (1.6 × 10-12 cm3 s-1 at 298 K; Ea = - 2.80 kcal mol-1) are in reasonable agreement with the experimental results. The experimental and theoretical results of the reaction of CH2OO with CH3SH are compared to the reactions of CH2OO with methanol and hydrogen sulfide, and the trends in reactivity are discussed. The results of the present work indicate that this reaction has a negligible influence to atmospheric CH2OO or CH3SH.

External-forcing modulation on temporal variations of hydrothermalism-evidence from sediment cores in a submarine venting field off northeastern Taiwan.

The temporal variation of sulfur and metals in core sediments off Kueishantao Islet, a hydrothermal vent site at northeastern Taiwan, was explored to elucidate the changes in submarine hydrothermal emanation over a centennial time scale. The discharge of acidic fluids containing abundant sulfides and dissolved metals results in different concentrations of sulfur and metal accumulating in deposited sediments. In addition to particle size and organic carbon affecting metal contents, the content of total sulfur (TS), which is regarded as an indicator of hydrothermalism, correlates positively and strongly with Fe and other metals; however, it correlates negatively with another index of hydrothermalism, the Al/(Al+Fe+Mn) ratio. The TS content in Core Ks2, the core closest to the vents, increased during 1950-1956, 1968-1970, 1982-1987, 1990-1992, and 2004-2005, but decreased during 1967-1968, 1988-1990, and 1994-1995. The chronological changes in the TS concentration of Cores Ks3 and S2 were very similar to those of Core Ks2 within the aforementioned time spans. The numerous large earthquakes (ML > 5) and typhoons that affect northeastern Taiwan appear to influence hydrothermal emanation and determine the temporal variation of sulfur and metals in sediment cores.

Absolute Infrared Absorption Cross Section of the Simplest Criegee Intermediate Near 1285.7 cm-1.

The ν4 fundamental of the simplest Criegee intermediate, CH2OO, has been monitored with high-resolution infrared (IR) transient absorption spectroscopy under total pressures of 4-94 Torr. This IR spectrum provides an unambiguous identification of CH2OO and is potentially useful to determine the number density of CH2OO in various laboratory studies. Here we utilized an ultraviolet (UV) and IR coupled spectrometer to measure the UV and IR absorption spectra of CH2OO simultaneously; the absolute IR cross section can then be determined by using a known UV cross section. Due to significant pressure broadening in the studied pressure range, we integrated the IR absorption spectra between 1285.2 and 1286.4 cm-1 (covering the Q branch), and then we converted this integrated absorbance to the absolute integral IR cross section of CH2OO (for the Q branch); its absolute value is (3.7 ± 0.6) × 10-19 cm·molecule-1 or 2.2 ± 0.4 km·mol-1. The whole rotational band (P, Q, and R branches) can be adequately simulated by using the precise spectroscopic parameters from the literature, yielding the absolute integral IR cross section (full ν4 band) to be 19.2 ± 3.5 km·mol-1. For a practical detection of CH2OO, this work also reports the peak cross section as a function of total pressure (4-94 Torr O2). At low pressure (≤4 Torr), where the pressure broadening is insignificant, the absorption cross section of the highest peak is (6.2 ± 0.9) × 10-18 cm2·molecule-1 (at the system line width of 0.004 cm-1 fwhm).

Kinetics of the simplest Criegee intermediate reaction with ozone studied using a mid-infrared quantum cascade laser spectrometer.

The kinetics of the reaction of CH2OO with ozone has been studied by monitoring CH2OO using time-resolved infrared (IR) absorption spectroscopy, which utilized the fast chirped IR pulse train from a quantum cascade laser [J. Chem. Phys., 2017, 146, 244302]. CH2OO was prepared by photolyzing a gas mixture of CH2I2/O2/O3 at 352 nm; the photolysis wavelength was chosen to minimize the photodissociation of O3. The measured rate coefficient at 298 K and 30 Torr is (6.7 ± 0.5) × 10-14 cm3 s-1, independent of pressure from 30 to 100 Torr. The result indicates that previous ab initio calculations either underestimated or overestimated this reaction rate by one order of magnitude or more. The result also implies that, the reaction of the Criegee intermediate with ozone may play a role in laboratory studies of ozonolysis of alkenes. However, this reaction would not compete with other CH2OO sinks in the atmosphere.

High resolution quantum cascade laser spectroscopy of the simplest Criegee intermediate, CH2OO, between 1273 cm-1 and 1290 cm-1.

The region 1273-1290 cm-1 of the ν4 fundamental of the simplest Criegee intermediate, CH2OO, has been measured using a quantum cascade laser transient absorption spectrometer, which offers greater sensitivity and spectral resolution (<0.004 cm-1) than previous works based on thermal light sources. Gas phase CH2OO was generated from the reaction of CH2I + O2 at 298 K and 4 Torr. The analysis of the absorption spectrum has provided precise values for the vibrational frequency and the rotational constants, with fitting errors of a few MHz. The determined ratios of the rotational constants, A'/A″ = 0.9986, B'/B″ = 0.9974, and C'/C″ = 1.0010, and the relative intensities of the a- and b-type transitions, 90:10, are in good agreement with literature values from a theoretical calculation using the MULTIMODE approach, based on a high-level ab initio potential energy surface. The low-K (=Ka) lines can be fitted extremely well, but rotational perturbations by other vibrational modes disrupt the structure for K = 4 and K ≥ 6. Not only the spectral resolution but also the detection sensitivity of CH2OO IR transitions has been greatly improved in this work, allowing for unambiguous monitoring of CH2OO in kinetic studies at low concentrations.

Distribution of organic carbon and lignin in soils in a subtropical small mountainous river basin.

As a unique biomarker of terrigenous organic matter (OM), lignin has provided valuable information for tracing the sources of OM in land to ocean transfer. Oceanian small mountainous rivers (SMRs) are characterized by extremely high erosional rate and quick change in microclimate within watershed, which may potentially affect the distribution of soil OC and lignin concentrations and compositions. Bulk OC% and lignin were determined on surface soils and soil profiles from a Taiwanese SMR (Jhuoshuei River) and nearby region along a large altitudinal gradient (3-3176 m) to investigate the influence of microclimate on soil OC and lignin. Both surface soils OC% and lignin increased in higher altitude, suggesting higher preservation of OM in the cold region. Variations in lignin vegetation indices (S/V and C/V) in surface soils generally reflect the vegetation change in this river basin, and were more affected by precipitation seasonality than mean annual precipitation. Lignin concentration decreased with depth, along with a decrease in S/V and C/V and an increase in degradation indices ((Ad/Al)v and DHBA/V), reflecting a decreased input and/or biodegradation of lignin in subsoils. Our survey on soil lignin in Taiwan SMR provided the basis for utilizing lignin to trace the source of OC in land to ocean transfer as well as paleo-climate and paleo-vegetation reconstruction study in Taiwan SMRs.

Distribution, mass inventories, and ecological risk assessment of legacy and emerging contaminants in sediments from the Pearl River Estuary in China.

This study focused on comparing the occurrences and environmental toxic risks for diverse priority and emerging contaminants (>100 chemicals) in the sediments from the Pearl River Estuary (PRE, China). The most predominant compounds were cationic surfactants, organophosphate flame retardants (e.g., triisobutylphosphate), and polycyclic aromatic hydrocarbons (PAHs), accounting for >75% of the total mass inventory (∼330 metric tons). Wastewater discharges seem to be one of the main sources of pollution in the area, as the highest concentrations (>1000ngg-1 for some chemicals) were reported in the upper part of the PRE (near Guangzhou city) and Macau. Highest levels of ultraviolet (UV) filters, however, were observed in recreational areas, revealing the importance of direct sources (e.g., outdoor activities). An environmental risk assessment showed that PAHs and dichlorodiphenyl dichloroethylene had the highest hazard quotient (HQ) values (up to 233). Nonylphenol, a metabolite from nonionic surfactant, and two UV filters (2-ethyl-hexyl-4-trimethoxycinnamate and 4-methylbenzylidene camphor) also posed a significant threat to benthic species (HQ>1). Further research through the realization of monitoring campaigns and toxicity tests is encouraged, as the exposure of the resident aquatic organisms and human population to these and other emerging chemicals is expected to increase over the years.

Separating para and ortho water.

Water exists as two nuclear-spin isomers, para and ortho, determined by the overall spin of its two hydrogen nuclei. For isolated water molecules, the conversion between these isomers is forbidden and they act as different molecular species. Yet, these species are not readily separated, and no pure para sample has been produced. Accordingly, little is known about their specific physical and chemical properties, conversion mechanisms, or interactions. The production of isolated samples of both spin isomers is demonstrated in pure beams of para and ortho water in their respective absolute ground state. These single-quantum-state samples are ideal targets for unraveling spin-conversion mechanisms, for precision spectroscopy and fundamental symmetry-breaking studies, and for spin-enhanced applications, for example laboratory astrophysics and astrochemistry or hypersensitized NMR experiments.

Chemical reactions of conformationally selected 3-aminophenol molecules in a beam with Coulomb-crystallized Ca+ ions.

Many molecules exhibit multiple conformers that often easily interconvert under thermal conditions. Therefore, single conformations are difficult to isolate which renders the study of their distinct chemical reactivities challenging. We have recently reported a new experimental method for the characterization of conformer-specific effects in chemical reactions [Y.-P. Chang, K. Dlugolecki, J. Küpper, D. Rösch, D. Wild, and S. Willitsch, "Specific chemical reactivities of spatially separated 3-aminophenol conformers with cold Ca(+) ions," Science 342, 98-101 (2013)]. Different conformers are spatially separated using inhomogeneous electric fields and reacted with a Coulomb crystal of cold, spatially localized ions in a trap. As a first application, we studied reactions between the two conformers of 3-aminophenol and Ca(+). We observed a twofold larger rate constant for the cis compared to the trans conformer which was rationalized in terms of the differences in the long-range ion-molecule interactions. The present article provides a detailed description of the new method and a full account of the experimental results as well as the accompanying theoretical calculations.

Spatial separation of molecular conformers and clusters.

Gas-phase molecular physics and physical chemistry experiments commonly use supersonic expansions through pulsed valves for the production of cold molecular beams. However, these beams often contain multiple conformers and clusters, even at low rotational temperatures. We present an experimental methodology that allows the spatial separation of these constituent parts of a molecular beam expansion. Using an electric deflector the beam is separated by its mass-to-dipole moment ratio, analogous to a bender or an electric sector mass spectrometer spatially dispersing charged molecules on the basis of their mass-to-charge ratio. This deflector exploits the Stark effect in an inhomogeneous electric field and allows the separation of individual species of polar neutral molecules and clusters. It furthermore allows the selection of the coldest part of a molecular beam, as low-energy rotational quantum states generally experience the largest deflection. Different structural isomers (conformers) of a species can be separated due to the different arrangement of functional groups, which leads to distinct dipole moments. These are exploited by the electrostatic deflector for the production of a conformationally pure sample from a molecular beam. Similarly, specific cluster stoichiometries can be selected, as the mass and dipole moment of a given cluster depends on the degree of solvation around the parent molecule. This allows experiments on specific cluster sizes and structures, enabling the systematic study of solvation of neutral molecules.

Specific chemical reactivities of spatially separated 3-aminophenol conformers with cold Ca+ ions.

Many molecules exhibit multiple rotational isomers (conformers) that interconvert thermally and are difficult to isolate. Consequently, a precise characterization of their role in chemical reactions has proven challenging. We have probed the reactivity of specific conformers by using an experimental technique based on their spatial separation in a molecular beam by electrostatic deflection. The separated conformers react with a target of Coulomb-crystallized ions in a trap. In the reaction of Ca(+) with 3-aminophenol, we find a twofold larger rate constant for the cis compared with the trans conformer (differentiated by the O-H bond orientation). This result is explained by conformer-specific differences in the long-range ion-molecule interaction potentials. Our approach demonstrates the possibility of controlling reactivity through selection of conformational states.

Rotational and vibrational state distributions of NaH in the reactions of Na(4 (2)S,3 (2)D, and 6 (2)S) with H2: Insertion versus harpoon-type mechanisms.

By using a pump-probe technique, the nascent rotational and vibrational state distributions of NaH are obtained in the Na(4 (2)S,3 (2)D, and 6 (2)S) plus H(2) reactions. The rotational distributions for the Na(4 (2)S,3 (2)D) reactions yield a bimodal feature with a major component peaking at J=20-22, similar to that obtained previously in the 4 (2)P reaction, whereas the Na(6 (2)S) reaction gives rise to a distinct distribution with a much lower rotational temperature. The vibrational populations (v=0-4) for these 4 (2)S, 3 (2)D, and 6 (2)S reactions are characterized by corresponding temperatures of 1692+/-120, 819+/-35, and 5329+/-350 K. Due to a significant contribution of configurational mixing between different states with the same symmetry, the collision species initiated from the 4 (2)S and 3 (2)D states are anticipated to track along the entrance surface in a near C(2v) symmetry, then undergo nonadiabatic transition to the inner limb of the reactive 2A(') surface. In contrast, the reaction pathway for the Na(6 (2)S) state with a significantly reduced ionization energy is anticipated to follow a harpoon-type mechanism via a (near) collinear configuration. The increased atomic size of Na may hinder the insertion approach.

Photodissociation of 1,2-dibromoethylene at 248 nm: Br2 molecular elimination probed by cavity ring-down absorption spectroscopy.

The Br2 elimination channel is probed for 1,2-C2H2Br2 in the B(3)Pi(+)ou-X(1)Sigma(+)g transition upon irradiation at 248 nm by using cavity ring-down absorption spectroscopy (CRDS). The nascent vibrational population ratio of Br2(v=1)/Br2(v=0) is obtained to be 0.7+/-0.2, thus indicating that the Br2 fragment is produced in hot vibrational states. The obtained Br2 products are anticipated to result primarily from photodissociation of the ground-state cis isomer via four-center elimination or from cis/trans isomers via three-center elimination, each mechanism involving a transition state that has a Br-Br distance much larger than that of ground state Br2. According to ab initio potential energy calculations, the pathways that lead to Br2 elimination may proceed either through the electronic ground state by internal conversion or through the triplet state by intersystem crossing. Temperature-dependence measurements are examined, thereby supporting the pathway that involves internal conversion--which was excluded previously by using product translational spectroscopy (PTS). The quantum yield for the Br2 elimination reaction is determined to be 0.120.1, being substantially contributed by the ground-state Br2 product. The discrepancy of this value from that (of 0.2) obtained by PTS may rise from the lack of measurements in probing the triplet-state Br2 product.