Philip S. Stevens

Measurement of tropospheric OH and HO2 by laser-induced fluorescence at low pressure

The hydroxyl radical (OH) is the primary oxidant in the atmosphere, responsible for many photochemical reactions that affect both regional air quality and global climate change. Because of its high reactivity, abundances of OH in the troposphere are less than 1 part per trillion by volume (pptv) and thus difficult to measure accurately. This paper describes an instrument for the sensitive detection of OH in the troposphere using low-pressure laser-induced fluorescence. Ambient air is expanded into a low pressure detection chamber, and OH is both excited and detected using the A(sup 2) Epsilon(+)(v prime = 0) yields X(sup 2)Pi(v double prime = 0) transition near 308 nm. An injector upstream of the detection axis allows for the addition of reagent NO to convert ambient HO2 to OH using the fast reaction HO2 + NO yields OH + NO2. Using recent advances in laser and detector technologies, this prototype instrument is able to detect less than 1 x 10(exp 5) molecules/cu cm (0.004 pptv) of OH with an integration time of 30 s with negligible interferences.

Measurements of OH and HO 2 concentrations during the MCMA-2006 field campaign – Part 1: Deployment of the Indiana University laser-induced fluorescence instrument

Measurements of tropospheric hydroxyl (OH) and hydroperoxy (HO2) radicals were made during the MCMA (Mexico City Metropolitan Area) field campaign as part of the MILAGRO (Megacity Initiative: Local and Global Research Observations) project during March 2006. These radicals were measured using a laser-induced fluorescence instrument developed at Indiana University. This new instrument takes advantage of the Fluorescence Assay by Gas Expansion technique (FAGE) together with direct excitation and detection of OH at 308 nm. HO 2 is indirectly measured as OH by titration with NO inside the fluorescence cell. At this stage of development, IU-FAGE is capable of detecting 3.9×105 molecule/cm3 of both OH and HO2, with a signal to noise ratio of 1, an averaged laser power of 10-mW and an averaging time of 5-min. The calibration accuracies (1 σ) are±17% for OH and±18% for HO2 using the water-vapor photolysis/O2 actinometry calibration technique. OH and HO2 concentrations were successfully measured at an urban site in Mexico City, with observed concentrations comparable to those measured in other polluted environments. Enhanced levels of OH and HO 2 radicals were observed on several days between 09:30–11:00 a.m. and suggest an intense photochemistry during morning hours that may be due to elevated sources of HO x ( H+HO2) and a fast cycling between the radicals under the high NO x (NO+NO2) conditions of the MCMA. Correspondence to: S. Dusanter (sdusante@indiana.edu)

OH and HO2 measurements using laser‐induced fluorescence

During August and September 1993 a laser-induced fluorescence (LIF) instrument was used to observe OH and HO2 as part of the Tropospheric OH Photochemistry Experiment (TOHPE) in the mountains west of Boulder, Colorado. A prototype version of this instrument has been described previously. Modifications were made to the instrument for TOHPE, including the integration of a new dye laser. The instrument was calibrated by producing known amounts of OH and HO2 above the instrument inlet. HO2 was measured on 19 days during TOHPE, while OH was measured on 5 days. Although poor laser performance limited the detection limit to 1 to 2×l06 cm−3 for an integration time of 300 s and a signal-to-noise ratio of 1, OH concentrations were observed to reach 3 to 7×l06 cm−3 near midday. HO2 typically peaked near 1×108 cm−3. HO2 consistently reached its maximum near local noon. Observations made with the LIF instrument are compared with observations made with an ion-assisted technique.

Measuring OH and HO2 in the Troposphere by Laser-Induced Fluorescence at Low Pressure

Abstract The hydroxyl radical OH oxidizes many lime gases in the atmosphere. It initiates and then participates in chemical reactions that lead to such phenomena as photochemical smog, acid rain, and stratospheric ozone depletion. Because OH is so reactive, its volume mixing ratio is less than 1 part per trillion volume (pptv) throughout the troposphere. Its close chemical cousin, the hydroperoxyl radical HO2, participates in many reactions as well. The authors have developed an instrument capable of measuring OH and HO2 by laser-induced fluorescence in a detection chamber at low pressure. This prototype instrument is able to detect about 1.4 × 105 molecules cm−3 (0.005 pptv) of OH at the ground in a signal integration time of 30 s with negligible interferences. The absolute uncertainty is a factor of 1.5. This instrument is now being adapted to aircraft use for measurements throughout the troposphere.

Experimental and Ab Initio Dynamical Investigations of the Kinetics and Intramolecular Energy Transfer Mechanisms for the OH + 1,3-Butadiene Reaction between 263 and 423 K at Low Pressure

The rate constants for the reaction of the OH radical with 1,3-butadiene and its deuterated isotopomer has been measured at 1-6 Torr total pressure over the temperature range of 263-423 K using the discharge flow system coupled with resonance fluorescence/laser-induced fluorescence detection of OH. The measured rate constants for the OH + 1,3-butadiene and OH + 1,3-butadiene- d 6 reactions at room temperature were found to be (6.98 +/- 0.28) x 10 (-11) and (6.94 +/- 0.38) x 10 (-11) cm (3) molecule (-1) s (-1), respectively, in good agreement with previous measurements at higher pressures. An Arrhenius expression for this reaction was determined to be k 1 (II)( T) = (7.23 +/- 1.2) x10 (-11)exp[(664 +/- 49)/ T] cm (3) molecule (-1) s (-1) at 263-423 K. The reaction was found to be independent of pressure between 1 and 6 Torr and over the temperature range of 262- 423 K, in contrast to previous results for the OH + isoprene reaction under similar conditions. To help interpret these results, ab initio molecular dynamics results are presented where the intramolecular energy redistribution is analyzed for the product adducts formed in the OH + isoprene and OH + butadiene reactions.

Rate constants for the gas-phase reactions of OH and O3 with β-ocimene, β-myrcene, and α- and β-farnesene as a function of temperature.

The rate constants for the gas-phase reactions of hydroxyl radicals and ozone with the biogenic hydrocarbons β-ocimene, β-myrcene, and α- and β-farnesene were measured using the relative rate technique over the temperature ranges 313-423 (for OH) and 298-318 K (for O₃) at about 1 atm total pressure. The OH radicals were generated by photolysis of H₂O₂, and O₃ was produced from the electrolysis of O₂. Helium was used as the diluent gas. The reactants were detected by online mass spectrometry, which resulted in high time resolution, allowing large amounts of data to be collected and used in the determination of the Arrhenius parameters. The following Arrhenius expressions have been determined for these reactions (in units of cm³ molecules⁻¹ s⁻¹): for β-ocimene + OH, k = (4.35(-0.66)(+0.78)) × 10⁻¹¹ exp[(579 ± 59)/T]; for β-ocimene + O₃, k = (3.15(-0.95)(+1.36)) × 10⁻¹⁵ exp[-(626 ± 110)/T]; for β-myrcene + O₃, k = (2.21(-0.66)(+0.94)) × 10⁻¹⁵ exp[-(520 ± 109)/T]; for α-farnesene + OH, k(OH) = (2.19 ± 0.11) × 10⁻¹⁰ for 23-413 K; for α-farnesene + O₃, k = (3.52(-2.54)(+9.09)) × 10⁻¹² exp[-(2589 ± 393)/T]; for β-farnesene + OH, k(OH) = (2.88 ± 0.15) × 10⁻¹⁰ for 323-423 K; for β-farnesene + O₃, k = (1.81(-1.19)(+3.46)) × 10⁻¹² exp[-(2347 ± 329)/T]. The Arrhenius parameters here are the first to be reported. The reactions of α- and β-farnesene with OH showed no significant temperature dependence. Atmospheric residence times due to reactions with OH and O₃ were also presented.

Measurements of hydroxyl and hydroperoxy radicals during CalNex‐LA: Model comparisons and radical budgets

Measurements of hydroxyl (OH) and hydroperoxy (HO2*) radical concentrations were made at the Pasadena ground site during the CalNex-LA 2010 campaign using the laser-induced fluorescence-fluorescence assay by gas expansion technique. The measured concentrations of OH and HO2* exhibited a distinct weekend effect, with higher radical concentrations observed on the weekends corresponding to lower levels of nitrogen oxides (NOx). The radical measurements were compared to results from a zero-dimensional model using the Regional Atmospheric Chemical Mechanism-2 constrained by NOx and other measured trace gases. The chemical model overpredicted measured OH concentrations during the weekends by a factor of approximately 1.4 ± 0.3 (1σ), but the agreement was better during the weekdays (ratio of 1.0 ± 0.2). Model predicted HO2* concentrations underpredicted by a factor of 1.3 ± 0.2 on the weekends, while measured weekday concentrations were underpredicted by a factor of 3.0 ± 0.5. However, increasing the modeled OH reactivity to match the measured total OH reactivity improved the overall agreement for both OH and HO2* on all days. A radical budget analysis suggests that photolysis of carbonyls and formaldehyde together accounted for approximately 40% of radical initiation with photolysis of nitrous acid accounting for 30% at the measurement height and ozone photolysis contributing less than 20%. An analysis of the ozone production sensitivity reveals that during the week, ozone production was limited by volatile organic compounds throughout the day during the campaign but NOx limited during the afternoon on the weekends.

Influence of Water on Anharmonicity, Stability, and Vibrational Energy Distribution of Hydrogen-Bonded Adducts in Atmospheric Reactions: Case Study of the OH + Isoprene Reaction Intermediate Using Ab Initio Molecular Dynamics

The effect of water on the stability and vibrational states of a hydroxy-isoprene adduct is probed through the introduction of 1-15 water molecules. It is found that when a static nuclear harmonic approximation is invoked there is a substantial red-shift of the alcohol O-H stretch (of the order of 800 cm(-1)) as a result of introduction of water. When potential energy surface sampling and associated anharmonicities are introduced through finite temperature ab initio dynamics, this hydroxy-isoprene OH stretch strongly couples with all the water vibrational modes as well as the hydroxy-isoprene OH bend modes. A new computational technique is introduced to probe the coupling between these modes. The method involves a two-dimensional, time-frequency analysis of the finite temperature vibrational properties. Such an analysis not only provides information about the modes that are coupled as a result of finite-temperature analysis, but also the temporal evolution of such coupling.

Radical Dependence of the Yields of Methacrolein and Methyl Vinyl Ketone from the OH-Initiated Oxidation of Isoprene under NOx-Free Conditions

Formation yields of methacrolein (MAC), methyl vinyl ketone (MVK), and 3-methyl furan (3MF) from the hydroxyl radical (OH) initiated oxidation of isoprene were investigated under NO(x)-free conditions (NO(x) = NO + NO(2)) at 50 °C and 1 atm in a quartz reaction chamber coupled to a mass spectrometer. Yields of the primary products were measured at various OH and hydroperoxy (HO(2)) radical concentrations and were found to decrease as the HO(2)-to-isoprene-based peroxy radical (ISORO(2)) concentration ratio increases. This is likely the result of a competition between ISORO(2) self- and cross-reactions that lead to the formation of the primary products, with reactions between these peroxy radicals and HO(2) which can lead to the formation of peroxides. Under conditions with HO(2)/ISORO(2) ratios close to 0.1, yields of MVK (15.5% ± 1.4%) and MAC (13.0% ± 1.2%) were higher than the yields of MVK (8.9% ± 0.9%) and MAC (10.9% ± 1.1%) measured under conditions with HO(2)/ISORO(2) ratios close to 1. This radical dependence of the yields was reproduced reasonably well by an explicit model of isoprene oxidation, suggesting that the model is able to reproduce the observed products yields under a realistic range of atmospheric HO(2)/ISORO(2) ratios.

Experimental and Theoretical Studies of the Kinetics of the OH + Hydroxyacetone Reaction As a Function of Temperature

The rate constant for the reaction of the OH radical with hydroxyacetone was measured between 2 and 5 Torr and over the temperature range of 280-350 K, using a discharge-flow system coupled with resonance fluorescence detection of the OH radical. At 298 K the rate constant was found to be (3.02 +/- 0.28) x 10(-12) cm3 molecule(-1) s(-1), in excellent agreement with several previous studies. A positive temperature dependence was measured over the temperature range 280-350 K, described by the Arrhenius expression k = (1.88 +/- 0.75) x 10(-11) exp[-(545 +/- 60)/T] cm3 molecule(-1) s(-1), in contrast to previous measurements of the temperature dependence for this reaction and suggesting that the atmospheric lifetime of hydroxyacetone may be greater than previously estimated. Theoretical calculations of the potential energy surface for this reaction suggest that the mechanism for this reaction involves hydrogen abstraction through a hydrogen-bonded prereactive complex similar to the OH + acetone reaction, with a calculated barrier height between -1 and 1 kcal mol(-1) depending on the level of theory.