Effect of CH3OOH on the atmospheric concentration of OH radicals

Methyl hydroperoxide (CH₃OOH, MHP) is known to be a significant sink and reservoir of HO_x and RO_x radicals in the atmosphere. In order to investigate the impact of MHP on the concentration of atmospheric OH radicals, two key gas-phase reactions of MHP, i.e. the reactions with OH radicals and with UV photolysis, have been simulated at temperature of 293±2 K and total pressure of 1.01×10⁵ Pa, using the long path Fourier transform infrared (LP-FTIR) spectrometry. OH radicals are generated by the photolysis of O₃ in the presence of water vapor. Combined with the relative rate method, the reaction rate constant of MHP with OH radicals is determined to be (3.99±0.15)×10^-12 cm³?molecule^-1?s^-1, and thus the atmospheric lifetime of MHP is estimated at 2.9 days. Furthermore, from detailed analysis of the UV photolysis of MHP, the yield of OH radicals is obtained to be 0.91±0.04. Based on the MHP atmospheric lifetime and the yield of OH radicals, it is concluded that MHP plays an essential role in the redistribution of OH radicals in the troposphere.     

Effect of CH_3OOH on the atmospheric concentration of OH radicals

Peroxides play an i mportant role in atmosphericchemistry,because they are not only amongthe prin-ciple oxidants in the chemical conversion of O3andSO2,but also act as an atmospheric sink and tempo-rary reservoir for i mportant oxidizing radicals such asOH, HO2and RO2[1 ,2]. With the development ofmeasurement techniques , several organic peroxideswere identified in the atmosphere in addition to hy-drogen peroxide (H2O2)[3—5]. And among these or-ganic peroxides , methyl hydroperoxide ( MH…     

Smog chamber studies of ozone formation potentials for isopentane

The incremental reactivity and ozone formation potential of isopentane have been studied with chamber experiments and computer simulations. The chemical mechanism used in the computer simulations is an isopentane sub-mechanism from the Master Chemical Mechanism （MCM）. The results from the chamber experiments suggest that the MCM can well simulate i-C5H12-NOx chamber experiments. The heterogeneous reaction of NO2 and water is an important source for OH radicals in the chamber experiments. The photolysis of HONO is responsible for the initiation of isopentane in photochemical reactions. The reaction rate constant for NO2 → HONO was determined to be 3.9×10-4―5.9×10-3 min-1 by conducting 3 sets of CO-NOx-air irradiations. 5 sets of isopentane-NOx irradiations under different conditions were performed in our chamber. Compared with the experiment with a low relative humidity （RH）, an increase in RH can increase the reaction rate of NO2 with H2O, so that the peak ozone occurs earlier. When isopentane is predominant over NOx, the peak ozone concentration is largely dependent on NOx concentrations.     

Kinetic study of the reaction of chlorine atoms with 3-methyl-3-buten-1-ol

The reaction of a typical unsaturated alcohol, 3-methyl-3-buten-1-ol （MBO331）, with Cl atoms, was investigated for the first time. The reaction was investigated using discharged flow-tube coupled with electron impact mass spectrometer. The experiments were performed over the temperature range of 248 K-298 K and at pressure of 1 torr in He as the bath gas. The obtained kinetic data were used to derive the Arrhenius expression： k1 = （3.47 ± 1.21） × 10^-11 exp[（ 599 ±69）/7] cm^3 molecule^-1 s^-1. Finally, atmospheric lifetimes of the MBO331 with respect to OH radicals, NO3 radicals and CI atoms have been calculated and the atmospheric implications are considered briefly.     

UV/H2O2作用下冰中苯酚的光转化及其与羟基自由基的关系

在UV和H₂O₂作用下考察pH值、 光强、 H₂O₂初始浓度和无机离子等对冰中苯酚光解的影响, 并利用二甲基亚砜（DMSO）捕获体系中生成的
羟基自由基（·OH）研究·OH对冰中苯酚光解的影响. 实验结果表明: H₂O₂可显著促进冰中产生·OH及苯酚光解; 改变光强、 pH值和H₂O₂的初始浓度, 苯酚的光解率随体系中·OH浓度的增加而增大; 加入NO^-₂和NO^-₃可抑制体系中产生·OH及苯酚光解; 加入SO^2-₄不影响体系中·OH的产生及苯酚光解; 加入CO^2-₃和HCO^-₃可抑制体系中产生·OH, 但对苯酚光解影响较小, 这是由于体系中产生了其他自由基所致.     

Experimental investigation of incremental reactivity of di-tert-butyl peroxide

Large quantities of di-tert-butyl peroxide (DTBP) have been emitted into the troposphere due to human activities. Its role in the atmospheric photochemical reaction has not been understood. This study presents the results of the photochemical reactions of DTBP and NOx, which have been simulated in a self-made smog chamber under the temperature of (29±1)℃. Both the wall decays of ozone and NO2 could be neglected, compared to the results in simulative experiments. The effective intensity of UV light used in the experiments was 1.28×10-3 s-1, which was expressed by the rate constant of NO2 photolysis in purified air. The reaction mechanism was proposed according to our results and reports of other researchers. The maximum values of incremental reactivity (IR) in the three simulative ex- periments were 9.53×10-2, 5.23×10-2 and 3.78×10-2, respectively. The incremental reactivity decreased with the increase of initial concentrations of DTBP. The IR value of DTBP obtained in this study was comparable to that of acetylene reported in our previous research.     

Studies on kinetics of reactions between phycobiliproteins and hydroxyl radicals by a pulse radiolytic technique

Scavenging of hydroxyl radical (· OH) by phycobiliproteins (C-phycocyanin, Allophycocyanin and R-phycoerythrin) was studied by competitive kinetics methods. Hydroxyl radicals were generated from pulse radiolysis of aqueous systems saturated with nitrous oxide (N₂O). The experimental results indicated that the three types of phycobiliproteins are all strong scavengers of · OH, the rate constants are around (2.8-5.6)×10⁹ L · mol^-1 · s^-1.     

Investigation of the cross-reaction mechanism of C<Subscript>6</Subscript>H<Subscript>5</Subscript>F-HNO<Subscript>2</Subscript> aqueous solution irradiated at 355 nm by transient absorbance spectrum technique

The transient absorption spectrum technique was employed to investigate the cross-reaction mechanism of C6H5F-HNO2 aqueous solution irradiated at 355 nm. The characteristic and the kinetic parameters of transient species were also detected. Hydroxyl radical derived from the photolysis of HNO2 was added to monofluorobenzene with a second-order rate constant of （5.83±0.17）×10^9 L·mol^-1·s^-1 to form an adduct, C6H5F…OH, which was able to react with HNO2 as the main reaction pathway with a rate constant of （8.3±0.1）×10^7 L·mol^-1·s^-1. The C6F6…OH adduct can also be decayed by elimination of H2O to yield monofluorophenyl radical C6H4F-. By GC-MS technique, the final products were identified to be monofluorophenol, nitro-monofluorobenzene, nitro-monofluorophenol and para-fluorobiphenyl.     

The impact of HS radicals on the measured rate constant of H<Subscript>2</Subscript>S with OH radicals

The rate constant for the reaction of OH radicals and hydrogen sulfide (H₂S) was studied in different bath gases (including N₂, air, O₂ and He) by using relative technique at 298 K. The small difference of the measured rate constants between N₂ and those with the presence of O₂ suggested possible influence of HS self reaction. Further experiments with NO_x presence for scavenging HS demonstrated this assumption. The rate constant of (5.48±0.12) ×10^–12 cm³ molecule^–1 s^–1 obtained with 4.09 ×10^–4 mol m₃ NO presence may be accurate for estimating the atmospheric lifetime of H2S. The results provided circumstantial evidence that the rapid reaction of HS with N₂O is suspected.     

Positronium annihilation in oxygen and nitrogen mixture

Formed in silica aerogels, positronium annihilation in oxygen and nitrogen mixture is studied by a simple and convenient method. The results show that ortho-positronium (o-Ps) lifetime is significantly shortened when some oxygen is introduced into nitrogen gas and that the o-Ps collisional quenching rate for an oxygen molecule is (28.0±0.4) μs^?1·amagat^?1 (1 amagat = 2.69×10²⁵ m^?3). It is found that the o-Ps annihilation rate in oxygen of 1atm at room temperature is (25.5±0.5) μs^?1 and that the effective number of electrons per oxygen molecule available for 2γ annihilation of positron in the o-Ps is (34.6±0.4).     

Study on the reaction of carbon disulfide with hydroxyl radical in aqueous solution

Carbon disulfide is an important sulfur-containing compound in the environment, and its oxidation produces about 30% of the atmospheric COS[1]. In situ measure- ments show that CS2 is widespread in the sea surface wa- ters[2―4], and more recently, the continental water seems to be especially rich sources of CS2 due to industrial waste- water effluents. It is generally accepted that the ocean is an important source for atm. CS2, and Xie et al.[5] found that marine photochemical reaction of…     

The v-v energy transfer of highly vibrationally excited states (II)

The vibrational energy transfer from highly vibrationally excited CO to H₂O molecules is studied by time-resolved Fourier transform infrared emission spectroscopy (TR FTIR). Following the 193 nm laser photolysis of CHBr₃ and O₂ the secondary reactions generate CO(v). The infrared emission of CO(v → v−1) is detected by TR FTIR. The excitation of H₂O molecules is not observed. By the method of the spectral simulation and the differential technique, 8 rate constants for CO(v)/H₂O system are obtained: (1.7 ±0.1), (3.4 ±0.2), (6.2 ±0.4), (8.0 ±1.0), (9.0 ±2.0), (12 ±3), (16 ±4) and (18 ±7) (10¹³cm³ · molecule^-1· s^-1). At least two reasons lead to the efficient energy transfer. One is the contributions of the rotational energy to the vibational energy defect and the other is the result of the complex collision. With the SSH andab initio calculations, the quenching mechanism of CO(v) by H₂O is suggested.     

Rate constants for the reaction of ozone with <Emphasis Type="Italic">n</Emphasis>-butyl, <Emphasis Type="Italic">s</Emphasis>-butyl and <Emphasis Type="Italic">t</Emphasis>-butyl methyl sulfides

The rate constants for the ozone reactions with n-butyl methyl sulfide （n-BMS, CHaCH2CH2CH2SCH3）, sec-butyl methyl sulfide （s-BMS, CH3CH2（CH3）CHSCHa） and tert-butyl methyl sulfide （t-BMS, （CH3）3CSCH3） were measured using our smog chamber under supposedly pseudo-first-order conditions at 30002 K and 760 Torr. The experimental determined rate constants for n-butyl, s-butyl and t-butyl methyl sulfide are （1.23 ± 0.06）×10-19, （5.08 ± 0.19）×10-20 and （2.26 ± 0.14）×10-20 cm3 molecule-1· s-1, respectively. The reactivity-structure relationship of the reactions was discussed and used to illustrate the mechanism of the ozone reaction with thioethers. The results enrich the kinetics data of atmospheric chemistry.     

Formation of the inclusion complex of Orange II with β-Cyclodextrin and its photostability

Inclusion complex of Orange II with β-Cyclodextrin (β-CD) and the anti-photolysis effect under UV-light were investigated. The molar ratio of inclusion complex of β-Cyclodextrin and Orange II is 1∶1. The formation constantK = 1.236×10³ L/mol was determined by the UV and Fluorescence spectra respectively, which was quite in accordance with the calculation with a modified Benesi-Hildbrand equation. The inclusion complex was characterized by the IR spectra and the molar ratio of inclusion complex is 1∶1 too. The formation constantK = 1.266×10³ L/mol was determined by¹H NMR analysis and was nearly the same by UV and fluorescence spectra. The photocatalytic decolorization rate of Orange II solutions containing β-CD and TiO₂ was smaller by 51.9% than that of the Orange II solutions only containing TiO₂, while in the case of direct photolysis of Orange II solutions, β-CD can lower the photolysis rate by 48.1% under UV-light. This result indicates β-CD can inhibit the photolysis and photocatalytic decolorization of Orange II under UV-light. The β-CD inclusion complex was found to be persistent to UV-light photolysis. Foundation item: Supported by the National Natural Science Foundation of China (20177017) Biography: Lu Ping (1958), male. Associate professor, research direction: environmental photochemistry.     

Comparison of intestinal absorption of two insulinmimic vanadyl complexes using Caco-2 monolayers as model system

Intestinal absorption of two oxovanadium complexes, vanadyl acetylacetonate (VO(acac)2) and bis-(maltolato)-oxovanadium (VO(ma)2), has been compared using Caco-2 monolayers as a model system. The two compounds are similar in chemical structures but different in glucose-lowering effects. Our experimental results show that they are both transported via passive diffusion with apparent permeabilty coefficients (apical→basolateral) of (82.0 ± 6.7) ×10-7 and (14.6 ± 0.7) ×10-7 cm·s-1, respectively. This suggests that absorptivity of VO(acac)2 is much higher than that of VO(ma)2. This difference may be related to the metabolism of either compound, or its ligand, or both in the course of the transport. However, This difference in absorption will cause the great difference in bioavailability, which might account for better efficacy of VO(acac)2 than VO(ma)2 as the insulin-mimic agent.     

Biogeochemical sequestration of carbon within phytoliths of wetland plants: A case study of Xixi wetland, China

As an important long-term terrestrial carbon sequestration mechanism, biogeochemical sequestration of carbon within phytoliths may play a significant role in the global carbon cycle and climate change. The aim of this study is to explore the potential of carbon bio-sequestration within phytoliths produced by wetland plants. The results show that the occluded carbon content of phytoliths in wetland plants ranges from 0.49% to 3.97%, with a CV (coefficient of variation) value of 810%. The data also indicate that the phytolith-occluded carbon (PhytOC) content of biomass for wetland plants depends not only on the phytolith content of biomass, but also the efficiency of carbon occlusion within phytoliths during plant growth in herb-dominated fens. The fluxes of carbon bio-sequestration within phytoliths of herb-dominated fen plants range from 0.003 to 0.077 t CO2 equivalents t-e-CO2ha-1a-1 . In China, 0.04×106 to 1.05×106t CO2 equivalents per year may be sequestrated in phytoliths of herbaceous-dominated fen plants. Globally, taking a fen area of 1.48×108 ha and the largest phytolith carbon biosequestration flux (0.077 t-e-CO 2 ha-1a-1 ) for herb-dominated fen plants, about 1.14×10 7 t CO 2 equivalents per year would have been sequestrated in phytoliths of fen plants. If other wetland plants have similar PhytOC production flux with herb-dominated fen plants (0.077 t-e-CO2ha-1a-1 ), about 4.39×10 7 t-e-CO2a-1 may be sequestrated in the phytoliths of world wetland plants. The data indicate that the management of wetland ecosystems (e.g. selection of plant species) to maximize the production of PhytOC have the potential to bio-sequestrate considerable quantities of atmospheric CO2 .     

Thermoluminescence of Al2O3 crystals grown by temperature gradient techniques

Color center concentrations of the Al2O3 crystal grown by temperature gradient techniques were calculated from Gaussian fits to absorption spectra. The concentrations for F- and F + -centers at 204, 232, and 255 nm were determined to be 1.361×10 17 , 0.098×10 17 , and 0.325×10 17cm-3 , respectively. Studies have shown that the thermoluminescence (TL) glow curve exhibits a prominent 450 K peak that matches well the first-order fitting curve. The thermal activation energy E and frequency factor s of the trap were determined to be 0.94456±0.00545 eV and 5.8703×10 11 s-1 . With this theoretical analysis, a simple one-trap/one-center TL model is presented to provide a theoretical explanation of the TL process.     

Growth mechanism of liquid Hg/solid β-HgS metal-semiconductor heterostructures

Density functional theory (DFT) was utilized to simulate the reactions occurred in the mixture solution of cysteine and Hg(II) ions with the ratio < 2. Simulation result shows that Hg ions will coordinate to cysteine by the thiol groups with the form of S–Hg₂ and S–Hg₃, and moreover, the content of free Hg ions can only be reduced by these two forms. OH^? plays an important role in the growth of β-HgS, because its nucleophilic substitution reaction supplies plenty of Hg–S–Hg radicals, which will be adsorbed onto the surface of liquid mercury ball and form the precursor of β-HgS(111) plane. Three valent bonds adsorption of Hg–S–Hg radicals onto the surface of Hg ball has more adsorption energy (?32.768 kcal mol^?1) than that of two valent bond adsorption (?20.882 kcal mol^?1). Hg balls will stop growing after completely covered with Hg–S–Hg radicals and their size will be limited. The growth direction of β-HgS is parallel to the “repelling” force, that is [111] direction in β-HgS lattice. The calculated results are in good agreement with the experimental observations, demonstrating that the DFT method can be taken as a very useful tool to interpret the solution reactions that cannot be solved by conventional methods.     

A kinetic study of the reaction of ozone with ethylene in a smog chamber under atmospheric conditions

Ozone is one of the key species in the processes of atmospheric chemistry, which can be taken as an indicator of oxidation capacity in the troposphere. The reaction of ozone with reactive gases is an important process in the troposphere. Experimental simulation equipment of smog chamber for atmospheric reactions is used to study the reaction of ozone with ethylene in real atmospheric environment with ozone concentrations of 100―200 ppb. The concentrations of ozone and ethylene were moni-tored during the reaction with the combination of Model 49C-O_3 Analyzer and GC-FID. A rate constant of 1.01×10~(-18) (cm~3·mol~(-1)·s-(~1)) was obtained at 286.5 K, under condition of which the half-life of ozone was 88 min. The results obtained from our experiments are in excellent agreement with those reported previously by other researchers under extremely low pressure in terms of matrixisolation technology. This demonstrates that our equipment of smog chamber for atmospheric reactions is reliable, which can be used for further research of the processes of atmospheric reactions.     

Preparation and photocatalytic properties of ilmenite NiTiO<Subscript>3</Subscript> powders for degradation of humic acid in water

The powders of ilmenite structure NiTiO₃ were prepared by a modified Pechini process using tetrabutyl titanate and nickel acetate as raw materials, and using citric acid and ethanol as a chelating agent and a solvent respectively. The powder samples were characterized by thermogravimetric and differential thermal analysis (TG-DTA) and X-ray diffraction (XRD). The photocatalytic activity of NiTiO₃ under the irradiation of ultraviolet rays (UV) light was evaluated by degrading humic acid (HA) in water as a probe reaction. The possible photodegradation mechanism was studied by the examination of active species ·OH, ·O₂⁻, and holes (h⁺) through adding scavengers. The TG-DTA and XRD results indicated that the good crystal structure of ilmenite phase NiTiO₃ could be obtained when the Ni-Ti citrate complex was calcined at 600°C. The photocatalytic activity experiments indicated that NiTiO₃ had favourable photocatalytic activity under the irradiation of UV light, and the photocatalytic degradation rate of HA reached 95.3% after a 2.5 h reaction with the photocatalyst calcined at 600°C and a photocatalyst dosage of 0.4 g/L. The possible photocatalytic mechanism was deduced that holes (h⁺) and ·OH radicals are the major reactive active species in the photocatalytic reaction, and dissolved oxygen plays a weak role in the degradation of HA.