Kinetics of heterogeneous ozone reactions

Earlier results on ozone destruction on solid surfaces gave apparent first order kinetics. Estimating the reaction kinetics from our data on ozone destruction on various powders (silica-gel, alumina, wood ash, coal ash, Saharan sand, calcite), we found that only calcite and wood ash exhibited such a behaviour. Removal of ozone by other powders used showed two straight lines in ln c-t plot with two different half-lives, t'(1/2) < t'(1/2). Comparing the kinetic constants for ozone removal on silica-gel and that of ozone reactions with polynuclear aromatic hydrocarbons (PAHs) adsorbed in submonolayer coverage on the same powder, the first reaction seems to be more likely in the case of pyrene and particularly fluoranthene. Enhanced ozone destruction on airborne aerosols could be an additional reason for fluoranthene stability in the real atmosphere.     

Humic substances as catalysts in condensation reactions

Humic substances (HS) demonstrate appreciable impact on the rate of the condensation reactions as shown in the example of the reaction between hydrazine and 4-(dimethylamino)-benzaldhyde in an aquatic environment. The catalytic activity of HS has also been demonstrated in Knoevenagel and Claisen-Schmidt reactions for condensation of carbonyl compounds with CH acids. The aquatic fulvic acids are the most active in these reactions. The velocity of the studied reactions also depends on pH, temperature, the concentration and origin of HS used. A possible micellar and acid-base catalysis mechanism in aquatic media has been suggested.     

Light-absorbing aldol condensation products in acidic aerosols: Spectra,kinetics, and contribution to the absorption index

The radiative properties of aerosols that are transparent to light in the near-UV and visible, such as sulfate aerosols, can be dramatically modified when mixed with absorbing material such as soot. In a previous work we had shown that the aldol condensation of carbonyl compounds produces light-absorbing compounds in sulfuric acid solutions. In this work we report the spectroscopic and kinetic parameters necessary to estimate the effects of these reactions on the absorption index of sulfuric acid aerosols in the atmosphere. The absorption spectra obtained from the reactions of six different carbonyl compounds (acetaldehyde, acetone, propanal, butanal, 2-butanone, and trifluoroacetone) and their mixtures were compared over 190–1100 nm. The results indicated that most carbonyl compounds should be able to undergo aldol condensation. The products are oligomers absorbing light in the 300–500 nm region where few other compounds absorb, making them important for the radiative properties of aerosols. Kinetic experiments in 96–75 wt% H₂SO₄ solutions and between 273 and 314 K gave an activation energy for the rate constant of formation of the aldol products of acetaldehyde of −(70±15) kJ mol⁻¹ in 96 wt% solution and showed that the effect of acid concentration was exponential. A complete expression for this rate constant is proposed where the absolute value in 96 wt% H₂SO₄ and at 298 K is scaled to the Henry's law coefficient for acetaldehyde and the absorption cross-section for the aldol products assumed in this work. The absorption index of stratospheric sulfuric acid aerosols after a 2-year residence time was estimated to 2×10⁻⁴, optically equivalent to a content of 0.5% of soot and potentially significant for the radiative forcing of these aerosols and for satellite observations in channels where the aldol products absorb.     

Kinetics of IO radicals with C1, C2 aliphatic alcohols in tropospherically relevant conditions

Environmental Science and Pollution Research - Kinetics of the reaction of IO radicals with methanol (MeOH) and ethanol (EtOH) were experimentally studied in the gas phase using pulsed laser...     

Kinetics of OH radical reactions with dibenzo-p-dioxin and selected chlorinated dibenzo-p-dioxins

The pulsed laser photolysis/pulsed laser-induced fluorescence (PLP/PLIF) technique has been applied to obtain rate coefficients for OH + dioxin (DD) (k1), OH + 2-chlorodibenzo-p-dioxin (2-CDD) (k2), OH + 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD) (k3), OH + 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) (k4), OH + 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) (k5), OH + 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) (k6), and OH + octachlorodibenzo-p-dioxin (OCDD) (k7) over an extended range of temperature. The atmospheric pressure (740 +/- 10 Torr) rate measurements are characterized by the following Arrhenius parameters (in units of cm3 molecule(-1) s(-1), error limits are 1 omega): k1(326-907 K) = (1.70+/-0.22) x 10(-12)exp(979+/-55)/T, k2(346-905 K) = (2.79+/-0.27) x 10(-12)exp(784+/-54)/T, k3(400-927 K) = 10(-12)exp(742+/-67)/T, k4(390-769 K) = (1.10+/-0.10) x 10(-12)exp(569+/-53)/T, k5(379-931 K) = (1.02+/-0.10) x 10(-12)exp(580+/-68)/T, k6(409-936 K) = (1.66+/-0.38) x 10(-12)exp(713+/-114)/T, k7(514-928 K) = (3.18+/-0.54) x 10(-12)exp(-667+/-115)/T. The overall uncertainty in the measurements, taking into account systematic errors dominated by uncertainty in the substrate reactor concentration, range from a factor of 2 for DD, 2-CDD, 2,3-DCDD, 2,7-DCDD, and 2,8-DCDD to +/- a factor of 4 for 1,2,3,4-TCDD and OCDD. Negative activation energies characteristic of an OH addition mechanism were observed for k1-k6. k7 exhibited a positive activation energy. Cl substitution was found to reduce OH reactivity, as observed in prior studies at lower temperatures. At elevated temperatures (500 K < T < 500 K), there was no experimental evidence for a change in reaction mechanism from OH addition to H abstraction. Theoretical calculations suggest that H abstraction will dominate OH reactivity for most if not all dioxins (excluding OCDD) at combustion temperatures (>1000 K). For OCDD, the dominant reaction mechanism at all temperatures is OH addition followed by Cl elimination.     

Kinetics of the reactions of soot surface-bound polycyclic aromatic hydrocarbons with the OH radicals

The kinetics of the heterogeneous reaction of OH radicals with 15 polycyclic aromatic hydrocarbons (PAHs) present in laboratory generated simulated kerosene combustion soot was studied at T = 290 K in a low pressure discharge-flow reactor combined with an electron-impact mass spectrometer. The kinetics of soot-bound PAH consumption in reaction with OH were monitored using off-line HPLC measurements of their concentrations in soot samples as a function of time of exposure to OH. Concentration of OH radicals in the gas phase was measured by mass spectrometry. The first-order rate constants measured for the individual PAH at T = 290 K ranged from 0.02 to 0.04 s^?1 and were found to be independent of the OH concentration ([OH] = (0.34–2.5) × 10¹² molecule cm^?3) and of the molecular structure of the PAH. In addition, the uptake coefficient of OH on soot surface and the diffusion coefficient of OH in He were measured to be 0.19 ± 0.03 (calculated with geometric surface area) and (615 ± 80) Torr cm² s^?1, respectively. Comparison of the results on the PAH + OH reaction to those from previous studies carried out on different carbonaceous substrates, indicates probable dependence of the heterogeneous reactivity of PAH toward OH on the substrate nature. Rapid reaction with OH can be an important potential pathway of the atmospheric degradation of non-volatile PAH present mainly in the particulate phase in the atmosphere.     

Kinetics of the gas-phase reactions of NO3 radicals with ethyl acrylate,n-butyl acrylate,methyl methacrylate and ethyl methacrylate

The relative rate method has been used to determine the rate constants for the gas-phase reactions of NO₃ radicals with a series of acrylate esters: ethyl acrylate (k₁), n-butyl acrylate (k₂), methyl methacrylate (k₃) and ethyl methacrylate (k₄) at 298 ± 1 K and 760 Torr. The obtained rate constants are k₁ = (1.8 ± 0.25) × 10^?16 cm³ molecule^?1 s^?1, k₂ = (2.1 ± 0.33) × 10^?16 cm³ molecule^?1 s^?1, k₃ = (3.6 ± 1.2) × 10^?15 cm³ molecule^?1 s^?1, k₄ = (4.9 ± 1.7) × 10^?15 cm³ molecule^?1 s^?1. The experimental rate constants are in good agreement with theoretical rate constants calculated by an algorithm of the correlation between the rate constants and the orbital energies for the reactions of unsaturated VOCs with NO₃ radicals. In addition, the atmospheric lifetimes of the compound against NO₃ attack are estimated and the results show that NO₃ reactions contribute little to the atmospheric losses of acrylate esters except in polluted regions.     

Searching for evidence of acid-catalyzed enhancement of secondary organic aerosol formation using ambient aerosol data

Laboratory experiments suggest that strong acids promote formation of enhanced levels of secondary organic aerosol (SOA), and organic aerosols may contribute to the health impacts of fine PM. We report results from examining hourly speciated fine particle data for evidence of ambient aerosol acidity-catalyzed SOA formation, as indicated by larger increases in the concentrations of organic aerosol mass occurring on days and in locations where more acidic aerosol (lower NH₄⁺/SO₄⁼ molar ratios) exists. Data sets from the southeastern U.S. were examined for which hourly acidity of PM_2.5 aerosols could be estimated, and for which hourly organic carbon (OC) content had been measured simultaneously. Within-day organic aerosol changes during selected periods were statistically related to concurrent aerosol acidity levels estimated from nitrate-corrected ammonium-to-sulfate ratios. Data from the Look Rock, TN, TVA/IMPROVE site for mid-July to mid-August 2004 showed average compositions frequently as acidic as NH₄HSO₄, however, no apparent increases in OC levels with increasing aerosol acidity were observed, even when [OC] changes were compared with time-delayed aerosol acidity estimates. SEARCH network data (2003–2004) for rural Centreville, AL (CTR) and Yorkville, GA (YRK) sites were also examined. Warm-season acidity levels were higher at CTR than at YRK, and daytime levels exceeded those at night at both sites. At the YRK site no consistent positive correlations were found between changes in OC or TC levels and aerosol acidity, even with time lags up to 6 h. Aerosol acidity at this site, however, is relatively low due to nearby agricultural sources of NH₃. In contrast, during selected periods from April to October 2004, at CTR, 6-h lagged OC changes were weakly correlated with daytime, nitrate-corrected NH₄⁺/SO₄⁼ molar ratios, but distinguishing this apparent relationship from meteorological effects on measured OC levels is challenging.     

餐饮业油烟气中醛类化合物的荧光法测定

提出了餐饮业油烟气中醛类化合物的荧光测定方法。通过试验选择丙醇作为油烟气中醛类化合物的吸收剂。研究了Ｈａｎｔｚｓｃｈ反应在测定油烟气中醛类化合物时的反应条件。样品与荧光试剂等体积混合,在ｐＨ６．０的体系中,５７℃下反应１５ｍｉｎ。     

Copper-catalyzed chlorination and condensation of acetylene and dichloroacetylene

The chlorination and condensation of acetylene at low temperatures is demonstrated using copper chlorides as chlorinated agents coated to model borosilicate surfaces. Experiments with and without both a chlorine source and borosilicate surfaces indicate the absence of gas-phase and gas-surface reactions. Chlorination and condensation occur only in the presence of the copper catalyst. C₂ through C₈ organic products were observed in the effluent; PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed that is consistent with the observed product distributions. Similar experiments with dichloroacetylene indicate greater reactivity in the absence of the copper catalyst. Reaction is observed in the gas-phase and in the presence of borosilicate surfaces at low temperatures. The formation of hexachlorobenzene is only observed in the presence of a copper catalyst. PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed for the formation of hexachlorobenzene from dichloroacetylene.     

Particle size dependence of a condensation nuclei counter

The influence of the particle size on the concentration indicated by a condensation nuclei counter (Model Rich 100, Environment One Corp.) was determined experimentally. The particle size dependence of this device was measured using fairly monodisperse silver particles and an absolute photographic condensation nuclei counter. The absolute calibration factor of the condensation nuclei counter also changed when the particle size of an aerosol containing atmospheric and Bunsen nuclei was changed.     

Natural attenuation of diesel aliphatic hydrocarbons in contaminated agricultural soil

A diesel fuel spill at a concentration of 1 L m(-2) soil was simulated on a 12 m(2) plot of agricultural land, and natural attenuation of aliphatic hydrocarbons was monitored over a period of 400 days following the spill after which the aliphatic hydrocarbon concentrations were found to be below the legal contamination threshold for soil. The main fraction of these compounds (95%) remained at the surface layer (0-10 cm). Shortly after the spill (viz. between days 0 and 18), evaporation was the main origin of the dramatic decrease in pollutant concentrations in the soil. Thereafter, soil microorganisms used aliphatic hydrocarbons as sources of carbon and energy, as confirmed by the degradation ratios found. Soil quality indicators, soil microbial biomass and dehydrogenase activity, regained their original levels about 200 days after the spill.     

Statistical analysis of condensation nuclei measurements in northwestern Spain

Measurements of condensation nuclei (CN) were taken daily at Villanubla, Spain, 845 m above sea level, in the months of March and April, 1980. The results are analyzed considering the fit to different statistical distributions using various stratifications based on meteorological parameters.     

Determination of aldehydes and ketones in air samples using cryotrapping sampling

A cryotrapping sampling technique using glass traps cooled in liquid nitrogen for monitoring carbonyl compounds in air has been developed. Sampling was followed by derivatization by addition of acidified 2,4-dinitrophenyl hydrazine (DNPH) solution to the traps and an aliquot of the sample was analysed with a high performance liquid chromatograph system (HPLC), equipped with a diode array detector. The procedure was optimised concerning derivatization conditions and analytical parameters on formaldehyde, acetaldehyde, propanal, acetone, butanal and benzaldehyde. The technique was applied in monitoring their concentration in the urban atmosphere in Ljubljana.     

Quantum-chemical descriptors for estimating hemolytic activity of aliphatic and aromatic methacrylates

Methacrylates such as methyl methacrylate (6), triethyleneglycol dimethacrylate (5) and bisphenol A glycidyldimethacrylate, bis-GMA, (8) are widely used as materials in dental resins perturbation of the phosphatidylcholine-cholesterol interaction. Such effects of aromatic methacrylates may be involved in their marked hemolytic action.     

Comparison of analytical techniques for the determination of aldehydes in test chambers

The level of carbonyl compounds in indoor air is crucial due to possible health effects and the high prevalence of their potential sources. Therefore, selecting a convenient and rapid analytical technique for the reliable detection of carbonyl compound concentrations is important. The acetyl acetone (acac) method is a widely used standard procedure for detecting gaseous formaldehyde. For measuring formaldehyde along with other carbonyl compounds, the DNPH-method is commonly applied. The recommended procedure for measuring volatile organic compounds (VOCs) is sampling on Tenax TA, followed by thermal desorption and GC/MS analysis. In this study, different analytical techniques for the quantification of formaldehyde, pentanal, and hexanal are critically compared. It was found that the acac- and DNPH-method are in very good agreement for formaldehyde. In contrast, the DNPH-method significantly underestimates indoor air concentrations of the higher aldehydes in comparison to sampling on Tenax TA, although both methods are strongly correlated. The reported results are part of the EURIMA-WKI study on levels of indoor air pollutants resulting from construction, building materials and interior decoration.     

反渗透膜处理维生素C凝结水的最优工艺条件

针对维生素C生产工艺中产生的凝结水产量大、处理成本高、存储运输困难和营养物质含量偏低等问题,采用反渗透技术对VC凝结水进行处理。实验建立小试规模反渗透膜处理装置,采用无量纲化多元回归分析方法,分析了操作条件指标与渗透水评价指标两套指标体系之间的关系,定量评价了各个操作条件指标对渗透水评价指标的整体影响程度,并在此基础上研究了最佳操作条件的工艺参数。结果表明：建立的无量纲化多元回归分析方法切实有效,在正交实验设计水平范围内,压力、pH和回流比均是多目标系统的影响因子,操作条件指标对渗透水评价指标的整体影响程度大小顺序为：压力〉pH〉回流比〉温度,且各自影响程度所占比例分别为43．02％、29．01％、25．07％和2．89％。各个操作因子对多指标系统的影响是独立的。在只考虑系统收益而不考虑膜污染的情况下,最佳操作条件分别为：温度r=30．65,压力P=1．5MPa,回流比r=0．78,pH=7．475。