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Observing and Projecting the Lasting Fate of the Hunga Eruption on Atmospheric Water Vapor and Hydroxyl Radical

On 15th Jan. 2022 the submarine Hunga volcano erupted injecting approximately 0.5 Tg of sulfur dioxide into the stratosphere, but more significantly added 150-170 Tg of water vapor to the stratospheric background (over a 10% perturbation) in a matter of several hours. The sulfur dioxide rapidly converted to sulfate aerosol and along with water vapor, was transported around the Southern Hemisphere sub-tropics into midlatitudes and beyond with some transport into the Northern Hemisphere. With a much longer lifetime than sulfate aerosol, measurable water vapor mass anomalies have persisted with only small losses over more than 2 years since the eruption and are likely to continue above background for the remainder of the decade. Satellite measurements from limb and nadir viewing observing instruments provide the information needed to reasonably initialize the Hunga eruption in the Goddard Earth Observing System (GEOS) model using the “replay” framework coupled to the Global Modeling Initiative (GMI) stratosphere-troposphere chemical mechanism for the recent past and have continued the simulations into the future with the free running chemistry climate model (CCM). Using a number of model ensemble members together with the satellite observations, we quantify how the Hunga eruption is perturbing atmospheric composition and climate and projecting the influences to come as the enhanced water vapor continues in the stratosphere with only very slow removal mechanisms. Modeling suggests that the water rich eruption enhanced stratospheric hydroxyl radiacal (OH) and is supported by the speed of the observed conversion of SO2 into sulfate aerosol. These simulations also suggest a significant reduction in tropospheric OH over the mid-high latitude Southern Hemisphere, which has implications for numerous species that are impacted by this radical. The Hunga eruption provides a useful test of chemistry climate models and an opportunity for observation-based process understanding and in making new connections.

Hunga volcano↗
NASA NTRS1990

Saturated fluorescence measurements of the hydroxyl radical in laminar high-pressure flames

The efficacy of laser saturated fluorescence (LSF) for OH concentration measurements in high pressure flames was studied theoretically and experimentally. Using a numerical model describing the interaction of hydroxyl with nonuniform laser excitation, the effect of pressure on the validity of the balanced cross-rate model was studied along with the sensitivity of the depopulation of the laser-coupled levels to the ratio of rate coefficients describing: (1) electronic quenching to (sup 2) Sigma (+) (v double prime greater than 0), and (2) vibrational relaxation from v double prime greater than 0 to v double prime = 0. At sufficiently high pressures and near-saturated conditions, the total population of the laser-coupled levels reaches an asymptotic value, which is insensitive to the degree of saturation. When the ratio of electronic quenching to vibrational relaxation is small and the rate of coefficients for rotational transfer in the ground and excited electronic states are nearly the same, the balanced cross-rate model remains a good approximation for all pressures. When the above ratio is large, depopulation of the laser-coupled levels becomes significant at high pressures, and thus the balanced cross-rate model no longer holds. Under these conditions, however, knowledge of the depletion of the laser-coupled levels can be used to correct the model. A combustion facility for operation up to 20 atm was developed to allow LSF measurements of OH in high pressure flames. Using this facility, partial saturation in laminar high pressure (less than or equal to 12.3 atm) C2H6/O2/N2 flames was achieved. To evaluate the limits of the balanced cross-rate model, absorption and calibrated LSF measurements at 3.1 and 6.1 atm were compared. The fluorescence voltages were calibrated with absorption measurements in an atmospheric flame and corrected for their finite sensitivity to quenching with: (1) estimated quenching rate coefficients, and (2) an in situ measurement from a technique employing two fluorescence detection geometries.

Carter, Campbell D.↗
NASA NTRS1980

Rate constant for the reaction of hydroxyl radical with formaldehyde over the temperature range 228-362 K

Absolute rate constants for the reaction OH ? H2CO measured over the temperature range 228-362 K using the flash photolysis-resonance fluorescence technique are given. The results are independent of variations in H2CO concentration, total pressure Ar concentration, and flash intensity (i.e., initial OH concentration). The rate constant is found to be invariant with temperature in this range, the best representation being k sub 1 = (1.05 ? or - 0.11) x 10 to the 11th power cu cm molecule(-1) s(-1) where the error is two standard deviations. This result is compared with previous absolute and relative determinations of k sub 1. The reaction is also discussed from a theoretical point of view.

Stief, L. J.↗
NASA NTRS1980

Rate constant for the reaction of hydroxyl radical with formaldehyde over the temperature range 228-362 K

Absolute rate constants for the reaction OH + H2CO have been measured over the temperature range 228-362 K using the flash photolysis-resonance fluorescence technique. The results were independent of variations in forbidden H2CO, total pressure of forbidden Ar and flash intensity (i.e., initial forbidden OH). The rate constant was found to be invariant with temperature in this range, the best representation being k1 = (1.05 + or - 0.11) x 10 to the -11th cu cm/molecule sec where the error is two standard deviations. This result is compared with previous absolute and relative determinations of k1. The reaction is also discussed from a theoretical point of view.

Stief, L. J.↗
NASA NTRS1981

Stratospheric hydroxyl radical concentrations - New limitations suggested by observations of gaseous and particulate sulfur

A one-dimensional aerosol model is employed in investigating the sensitivity of the stratospheric distributions of gaseous sulfur compounds and sulfate aerosol particles to changes in OH and CS2 concentrations, in eddy diffusion coefficients, and in important chemical rate constants. By comparing model predictions with recent observational data for SO2, OCS, and particulates, it is found that, with regard to atmospheric sulfur, CS2 is only a secondary source of sulfur for the stratosphere relative to OCS and that background tropospheric CS2 concentrations by volume are likely to be less than 70 parts per trillion. It is also established that under stratospheric conditions the rate coefficients for the reactions of OH with OCS and CS2 may be substantially smaller than the room temperature laboratory values of Kurylo (1978).

Turco, R. P.↗
NASA NTRS1983

Comments on laser-excited fluorescence of the hydroxyl radical: Relaxation coefficients at atmospheric pressure, appendix 5

The lifetime of the excited state of a atom or molecule is often determined from the rate of fluorescence decay originating as a function of buffer gas pressure, an accurate determination is made of the rates of collision induced transitions away from the excited state. Deconvolution can in principle be employed to resolve fluorescence times shorter than the response times of the system. However, attainable reproducibility and accuracy in actual experiments usually set a limit beyond which no meaningful results are expected. Prudence thus dictates that the results of deconvolution be viewed with extreme caution whenever fluorescence time much shorter than the response of times of the system are indicated.

Wang, C. C.↗
NASA NTRS1984

Mechanism of the atmospheric oxidation of sulfur dioxide - Catalysis by hydroxyl radicals

A flash photolysis/resonance fluorescence technique was used to investigate the decay of OH due to the reaction OH + SO2 (+M) to HOSO2 (+M). In the presence of small amounts of NO (10 to the 14th per cu cm), the decays deviated from the normal semilogarithmic linearity due to reformation of OH. On the basis of computer simulations of the decay curves, it is suggested that the reactions HOSO2 + O2 to HO2 + SO3 (k3), and HO2 + HO to OH + NO2 are the likely subsequent steps in SO2 oxidation. The upper limit for the binding energy of HOSO2 relative to OH + SO2 is estimated to be 32 kcal/mol. The atmospheric implications of a catalytic oxidation mechanism are briefly discussed.

Margitan, J. J.↗
NASA NTRS1991

Photodissociation of the hydroxyl radical (OH) at 157 nm

The photodissociation of the OH radical was studied at 157 nm via the detection of the product H atoms with the resonance fluorescence technique. OH radicals were produced in a fast-flow cell from the reaction between H and NO2 and subsequently photodissociated by an excimer laser operating on the F2 emission. The quantum yield for photodissociation of OH was measured to be 1.10 + or - 0.28. The photodissociation cross section was calculated to be 6.6 x 10 to the -18th sq cm (+ or - 25 percent).

Cody, R. J.↗
NASA NTRS1992

Global average concentration and trend for hydroxyl radicals deduced from ALE/GAGE trichloroethane (methyl chloroform) data for 1978-1990

An optimal estimation inversion scheme is utilized with atmospheric data and emission estimates to determined the globally averaged CH3CCl3 tropospheric lifetime and OH concentration. The data are taken from atmospheric measurements from surface stations of 1,1,1-trichloroethane and show an annual increase of 4.4 +/- 0.2 percent. Industrial emission estimates and a small oceanic loss rate are included, and the OH concentration for the same period (1978-1990) are incorporated at 1.0 +/- 0.8 percent/yr. The positive OH trend is consistent with theories regarding OH and ozone trends with respect to land use and global warming. Attention is given to the effects of the ENSO on the CH3CCl3 data and the assumption of continuing current industrial anthropogenic emissions. A novel tropical atmospheric tracer-transport mechanism is noted with respect to the CH3CCl3 data.

Prinn, R.↗
NASA NTRS1992

Saturated fluorescence measurements of the hydroxyl radical in laminar high-pressure C2H6/O2/N2 flames

Saturation of a transition of the OH molecule in high-pressure flames is demonstrated by obtaining saturation curves in C2H6/O2/N2 laminar flames at 1, 6.1, 9.2, and 12.3 atm. Quantitative fluorescence measurements of OH number density at pressures to 12.3 atm are presented. To assess the efficacy of the balanced cross-rate model for high-pressure flames, laser-saturated fluorescence measurements, which were calibrated in an atmospheric-pressure flame, are compared with absorption measurements at 3.1 and 6.1 atm. At 3.1 atm the absorption and fluorescence measurements compare well. At 6.1 atm, however, the concentrations given by lasre-saturated fluorescence are about 25 percent lower than the absorption values, indicating some depletion of the laser-coupled levels beyond that at atmospheric pressure. By using a reasonable estimate for the finite sensitivity to quenching, it is anticipated that fluorescence measurements that are calibrated at 1 atm can be applied to flames at about 10 atm with absolute errors within +/- 50 percent.

Carter, Campbell D.↗
NASA NTRS1993

Velocity distributions of hydrogen atoms and hydroxyl radicals produced through solar photodissociation of water

The velocity distributions of H and OH fragments produced through solar photodissociation of gaseous H2O molecules under collisionless conditions are presented. The calculations are carried out using: the most recently available absolute partial cross sections for the production of H and OH through photodissociation of H2O from its absorption onset at 1860 A down to 500 A; the newly available vibrational and rotational energy distributions of both the excited and ground state OH photofragments; the calculated cross sections for the total dissociation processes; and the integrated solar flux in 10 A increments from 500 to 1860 A in the continuum regions and the specific wavelength and flux at the bright solar lines. The calculated results show that the H atoms and the OH radicals produced exhibit multiple velocity groups. Since most current cometary modeling uses a single velocity of 20 km/sec associated with the photodissociation of H2O, the present results may be useful in interpreting the many peaks observed in the velocity distributions of the H Lyman alpha and H alpha of comets.

Wu, C. Y. R.↗
NASA NTRS1993

Detection of the hydroxyl radical in the Saturn magnetosphere

The detection of neutral OH molecules near the orbit of Tethys is reported. The findings suggest that neutral OH is one of the dominant species in Saturn's inner magnetosphere, implying a source rate for H2O 20 times greater than current theoretical estimates. One possible explanation is that the micrometeorite erosion rates of the inner satellites are significantly higher than expected.

Shemansky, D. E.↗
NASA NTRS1993

Rates of hydroxyl radical reactions with some HFCs

Relative rate constants for OH reactions with some HFCs have been determined at 298 K by a technique which measures the loss of HFC greater than OH. The following ratios were determine: k(152a)/k(CH4) = 5.2 +/- 0.5, k(CH4)/k(125) = 3.9 +/- 0.5, k(CH4)/k(134a) = 2.1 +/- 0.2, k(134a)/k(125) = 2.0 +/- 0.2, and k(C2H6)/k(152a) = 6.2 +/- 1.0. These results are in good agreement with literature values for the absolute rate constants except for HFC 134a, where a slower rate constant is indicated.

Demore, William B.↗
NASA NTRS1994

The active titration method for measuring local hydroxyl radical concentration

We are developing a method for measuring ambient OH by monitoring its rate of reaction with a chemical species. Our technique involves the local, instantaneous release of a mixture of saturated cyclic hydrocarbons (titrants) and perfluorocarbons (dispersants). These species must not normally be present in ambient air above the part per trillion concentration. We then track the mixture downwind using a real-time portable ECD tracer instrument. We collect air samples in canisters every few minutes for roughly one hour. We then return to the laboratory and analyze our air samples to determine the ratios of the titrant to dispersant concentrations. The trends in these ratios give us the ambient OH concentration from the relation: dlnR/dt = -k(OH). A successful measurement of OH requires that the trends in these ratios be measureable. We must not perturb ambient OH concentrations. The titrant to dispersant ratio must be spatially invariant. Finally, heterogeneous reactions of our titrant and dispersant species must be negligible relative to the titrant reaction with OH. We have conducted laboratory studies of our ability to measure the titrant to dispersant ratios as a function of concentration down to the few part per trillion concentration. We have subsequently used these results in a gaussian puff model to estimate our expected uncertainty in a field measurement of OH. Our results indicate that under a range of atmospheric conditions we expect to be able to measure OH with a sensitivity of 3x10(exp 5) cm(exp -3). In our most optimistic scenarios, we obtain a sensitivity of 1x10(exp 5) cm(exp -3). These sensitivity values reflect our anticipated ability to measure the ratio trends. However, because we are also using a rate constant to obtain our (OH) from this ratio trend, our accuracy cannot be better than that of the rate constant, which we expect to be about 20 percent.

Sprengnether, Michele↗
NASA NTRS1995

Rate constants and temperature dependences for the reactions of hydroxyl radical with several halogenated methanes, ethanes, and propanes by relative rate measurements

Rate constants of 15 OH reactions with halogen-substituted alkanes, C1 to C3, were studied using a relative rate technique in the temperature range 283-403 K. Compounds studied were CHF2Cl (22), CHF2Br (22B), CH3F (41), CH2F2 (32), CHF3 (23), CHClFCCl2F (122a), CHCl2CF3 (123), CHClFCF3 (124), CH3CF3 (143a), CH3CH2F (161), CF3CHFCF3 (227ea), CF3CH2CF3 (236fa), CF3CHFCHF2 (236ea), and CHF2CF2CH2F (245ca). Using CH4, CH3CCl3, CF3CF2H, and C2H6 as primary reference standards (JPL 92-20 rate constants), absolute rate constants are derived. Results are in good agreement with previous experimental results for six of the compounds studied, including CHF2Cl, CHF2Br, CH2F2, CH3CF3, CHFClCFCl2, and CF3CHFCF3. For the remainder the relative rate constants are lower than those derived from experiments in which OH loss was used to measure the reaction rate. Comparisons of the derived Arrhenius A factors with previous literature transition-state calculations show order of magnitude agreement in most cases. However, the experimental A factors show a much closer proportionality to the number of H atoms in the molecule than is evident from the transition state calculations. For most of the compounds studied, an A factor of (8 +/- 3)E-13 cm(exp 3)/(molecule s) per C-H bond is observed. A new measurement of the ratio k(CH3CCl3)/k(CH4) is reported that is in good agreement with previous data.

Hsu, K.-J.↗
NASA NTRS1995

Temperature-Dependent Rate Constants and Substituent Effects for the Reactions of Hydroxyl Radicals With Three Partially Fluorinated Ethers

Rate constants and temperature dependencies for the reactions of OH with CF3OCH3 (HFOC-143a), CF2HOCF2H (HFOC-134), and CF3OCF2H (HFOC-125) were studied using a relative rate technique in the temperature range 298-393 K. The following absolute rate constants were derived: HFOC-143a, 1.9E-12 exp(-1555/T); HFOC-134, 1.9E-12 exp(-2006/T); HFOC-125, 4.7E-13 exp(-2095/T). Units are cm(exp 3)molecule(exp -1) s(exp -1). Substituent effects on OH abstraction rate constants are discussed, and it is shown that the CF3O group has an effect on the OH rate constants similar to that of a fluorine atom. The effects are related to changes in the C-H bond energies of the reactants (and thereby the activation energies) rather than changes in the preexponential factors. On the basis of a correlation of rate constants with bond energies, the respective D(C-H) bond strengths in the three ethers are found to be 102, 104, and 106 kcal/mol, with an uncertainty of about 1 kcal/mol.

Hsu, K.-J.↗
NASA NTRS1996

Experimental and Estimated Rate Constants for the Reactions of Hydroxyl Radicals with Several Halocarbons

Relative rate experiments are used to measure rate constants and temperature dependencies of the reactions of OH with CH3F (41), CH2FCl (31), CH2BrCl (30B1), CH2Br2 (3OB2), CHBr3 (2OB3), CF2BrCHFCl (123aBl(alpha)), and CF2ClCHCl2 (122). Rate constants for additional compounds of these types are estimated using an empirical rate constant estimation method which is based on measured rate constants for a wide range of halocarbons. The experimental data are combined with the estimated and previously reported rate constants to illustrate the effects of F, Cl, and Br substitution on OH rate constants for a series of 19 halomethanes and 25 haloethanes. Application of the estimation technique is further illustrated for some higher hydrofluorocarbons (HFCs), including CHF2CF2CF2CF2H (338pcc), CF3CHFCHFCF2CF3 (43-10mee), CF3CH2CH2CF3 (356ffa), CF3CH2CF2CH2CF3 (458mfcf), CF3CH2CHF2 (245fa), and CF3CH2CF2CH3 (365mfc). The predictions are compared with literature data for these compounds.

DeMore, W.B.↗
NASA NTRS1995

Experimental and Estimated Rate Constants for the Reactions of Hydroxyl Radicals With Several Halocarbons

Relative rate experimental data are used to derive rate constants and temperature dependencies of the reactions of OH with several halocarbons. Rate constants for additional similar compounds are estimated. The experimental data, estimated data, and previously reported data are used to illustrate the effects of F, CL and Br substitution on OH rate constants for a series of 19 halomethanes and 25 haloethanes, as well as some higher HFCs.

hydroxy↗