Isoprene and Its Oxidation Products Methyl Vinyl Ketone, Methacrolein, and Isoprene Related Peroxides Measured Online over the Tropical Rain Forest of Surinam in March 1998

Airborne measurements of volatile organic compounds (VOC) were performed overthe tropical rainforest in Surinam (0–12 km altitude,2°–7° N, 54°–58° W) using the proton transferreaction mass spectrometry (PTR-MS) technique, which allows online monitoringof compounds like isoprene, its oxidation products methyl vinyl ketone,methacrolein, tentatively identified hydroxy-isoprene-hydroperoxides, andseveral other organic compounds. Isoprene volume mixing ratios (VMR) variedfrom below the detection limit at the highest altitudes to about 7 nmol/molin the planetary boundary layer shortly before sunset. Correlations betweenisoprene and its product compounds were made for different times of day andaltitudes, with the isoprene-hydroperoxides showing the highest correlation.Model calculated mixing ratios of the isoprene oxidation products using adetailed hydrocarbon oxidation mechanism, as well as the intercomparisonmeasurement with air samples collected during the flights in canisters andlater analysed with a GC-FID, showed good agreement with the PTR-MSmeasurements, in particular at the higher mixing ratios.Low OH concentrations in the range of 1–3 × 10⁵molecules cm^-3 averaged over 24 hours were calculated due to lossof OH and HO₂ in the isoprene oxidation chain, thereby stronglyenhancing the lifetime of gases in the forest boundary layer.     

Kinetics of the Gas-Phase Reactions of OH Radicals, NO3 Radicals and O3 with Three C7-Carbonyls Formed From The Atmospheric Reactions of Myrcene, Ocimene and Terpinolene

Rate constants for the gas-phase reactions of OH radicals, NO₃ radicals and O₃ with the C₇-carbonyl compounds 4-methylenehex-5-enal [CH₂=CHC(=CH₂)CH₂CH₂CHO], (3Z)- and (3E)-4-methylhexa-3,5-dienal [CH₂=CHC(CH₃)=CHCH₂CHO] and 4-methylcyclohex-3-en-1-one, which are products of the atmospheric degradations of myrcene, Z- and E-ocimene and terpinolene, respectively, have been measured at 296 ± 2 K and atmospheric pressure of air using relative rate methods. The rate constants obtained (in cm³ molecule^–1 s^–1 units) were: for 4-methylenehex-5-enal, (1.55 ± 0.15) × 10^–10, (4.75 ± 0.35) × 10^–13 and (1.46 ± 0.12) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; for (3Z)-4-methylhexa-3,5-dienal: (1.61 ± 0.35) × 10^–10, (2.17 ± 0.30) × 10^–12, and (4.13 ± 0.81) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; for (3E)-4-methylhexa-3,5-dienal: (2.52 ± 0.65) × 10^–10, (1.75 ± 0.27) × 10^–12, and (5.36 ± 0.28) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; and for 4-methylcyclohex-3-en-1-one: (1.10 ± 0.19) × 10^–10, (1.81 ± 0.35) × 10^–12, and (6.98 ± 0.40) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively. These carbonyl compounds are all reactive in the troposphere, with daytime reaction with the OH radical and nighttime reaction with the NO₃ radical being predicted to dominate as loss processes and with estimated lifetimes of about an hour or less.     

Tunable diode laser measurements of trace gases during the 1988 Polarstern cruise and intercomparisons with other methods

Measurements of NO₂, HCHO, and H₂O₂ were made by the highly specific method of mid infra-red absorption spectroscopy using tunable diode lasers (TDLAS) during the 1988 Polarstern expedition. The TDLAS data are compared to those obtained during the cruise using less direct methods. Southern Hemisphere NO₂ levels suggest nett photochemical destruction of O₃ in the boundary layer. Northern Hemisphere HCHO averaged 0.47±0.2 ppbv; the HCHO measurements are used in a simple calculation to estimate OH noontime maxima of 3–6×10⁶ cm^-3.     

Aqueous Phase Reaction of HNO4: The Impact on Tropospheric Chemistry

We use a global atmospheric chemistry transport model to study the possible influence of aqueous phase reactions of peroxynitric acid (HNO₄) on the concentrations and budgets of NO_x, SO_x, O₃ and H₂O₂. Laboratory studies have shown that the aqueous reaction of HNO_4aq withHSO^– _3aq, and the uni-molecular decomposition of the NO₄ ^– anion to form NO₂ ^– (nitrite) occur on a time scale of about a second. Despite a substantial contribution of the reaction of HSO^– _3aq with HNO_4aq to the overall in-cloud conversion of SO₂ to SO₄ ^2–, a simultaneous decrease of other oxidants (most notably H₂O₂) more than compensated the increase in SO₄ ^2– production. The strongest influence of heterogeneous HNO₄ chemistry was found in the boundary layer, where calculated monthly average ozone concentrations were reduced between 2% to 10% andchanges of H₂O₂ between –20% to +10%compared to a simulation which ignores this reaction. Furthermore, SO₂ was increased by 10% to 20% and SO₄ ^2–depleted by up to 10%. Since the resolution of our global model does not enable a detailed comparison with measurements in polluted regions, it is not possible to verify whether considering heterogeneous HNO₄ reactions results in a substantial improvement of atmospheric chemistry transport models. However, the conversion of HNO₄ in the aqueous phase seems to be efficient enough to warrant further laboratory investigations and more detailed model studies on this topic.     

An Assessment of HOx Chemistry in the Tropical Pacific Boundary Layer: Comparison of Model Simulations with Observations Recorded during PEM Tropics A

Reported are the results from a comparison of OH,H₂O₂CH₃OOH, and O₃ observationswithmodel predictions based on current HO_x–CH₄reaction mechanisms. The field observations are thoserecorded during the NASA GTE field program, PEM-Tropics A. The major focus ofthis paper is on thosedata generated on the NASA P-3B aircraft during a mission flown in the marineboundary layer (MBL) nearChristmas Island, a site located in the central equatorial Pacific (i.e.,2° N, 157° W). Taking advantage of thestability of the southeastern trade-winds, an air parcel was sampled in aLagrangian mode over a significantfraction of a solar day. Analyses of these data revealed excellent agreementbetween model simulated andobserved OH. In addition, the model simulations reproduced the major featuresin the observed diurnalprofiles of H₂O₂ and CH₃OOH. In the case ofO₃, the model captured the key observational feature whichinvolved an early morning maximum. An examination of the MBL HO_xbudget indicated that the O(¹D) + H₂Oreaction is the major source of HO_x while the major sinks involveboth physical and chemical processes involving the peroxide species,H₂O₂ and CH₃OOH. Overall, the generally goodagreement between modeland observations suggests that our current understanding ofHO_x–CH₄ chemistry in the tropical MBL isquite good; however, there remains a need to critically examine this chemistrywhen both CH₂O and HO₂are added to the species measured.     

Stratospheric N2O5, CH4, and N2O profiles from IR solar occultation spectra

Stratospheric volume mixing ratio profiles of N₂O₅, CH₄, and N₂O have been retrieved from a set of 0.052 cm^–1 resolution (FWHM) solar occultation spectra recorded at sunrise during a balloon flight from Aire sur l'Adour, France (44° N latitude) on 12 October 1990. The N₂O₅ results have been derived from measurements of the integrated absorption by the 1246 cm^–1 band. Assuming a total intensity of 4.32×10^–17 cm^–1/molecule cm^–2 independent of temperature, the retrieved N₂O₅ volume mixing ratios in ppbv (parts per billion by volume, 10^–9), interpolated to 2 km height spacings, are 1.64±0.49 at 37.5 km, 1.92±0.56 at 35.5 km, 2.06±0.47 at 33.5 km, 1.95±0.42 at 31.5 km, 1.60±0.33 at 29.5 km, 1.26±0.28 at 27.5 km, and 0.85±0.20 at 25.5 km. Error bars indicate the estimated 1- uncertainty including the error in the total band intensity (±20% has been assumed). The retrieved profiles are compared with previous measurements and photochemical model results.Laboratoire associé aux Universités Pierre et Marie Curie et Paris Sud.     

Atmospheric chemistry of the monoterpene reaction products nopinone,camphenilone, and 4-acetyl-1-methylcyclohexene

Rate constants for the gas-phase reactions of OH radicals with nopinone (6,6-dimethylbicyclo[3.1.1]heptan-2-one) and camphenilone (3,3-dimethylbicyclo[2.2.1]heptan-2-one) and for the reactions of 4-acetyl-1-methylcyclohexene with OH and NO₃ radicals and O₃ have been measured at 296±2 K. The rate constants (cm³ molecule^–1 s^–1 units) obtained were, for reaction with the OH radical: nopinone, (1.43±0.37)×10^–11; camphenilone, (5.15±1.44)×10^–12; and 4-acetyl-1-methylcyclohexene, (1.29±0.33)×10^–10; for reaction with the NO₃ radical: 4-acetyl-1-methylcyclohexene, (1.05±0.38)×10^–11; and for reaction with O₃: 4-acetyl-1-methylcyclohexene, (1.50±0.53)×10^–16. These data are used to calculate the tropospheric lifetimes of these monoterpene atmospheric reaction products.     

An Atmospheric Chemistry Interpretation of Mass Scans Obtained from a Proton Transfer Mass Spectrometer Flown over the Tropical Rainforest of Surinam

Data on a variety of organic gases are presented, obtained with a protontransfer mass spectrometer (PTR-MS) operated during the March 1998 LBA/CLAIREairborne measurement campaign, between 60 and 12500 m over the rainforest inSurinam (2° N–5° N, 54° W–57° W). The instrumentcan detect molecules with a proton affinity greater than water, includingalkenes, dialkenes, carbonyls, alcohols, and nitriles. Many such molecules areemitted from the rainforest (e.g., isoprene) or formed from the oxidation ofprimary emissions (e.g., methylvinylketone (MVK) and methacrolein (MACR)).From a comparison with modelled data; the variation with altitude; previouslyreported biogenic emissions and the time and location of the measurement,possible and probable identities for the significant masses encountered in therange 33–140 amu have been deduced.The main observed protonated masses, postulated identities and observedaverage boundary layer mixing ratios over the rainforest were: 33 methanol(1.1 nmol/mol); 42 acetonitrile (190 pmol/mol); 43 multiple possibilities (5.9nmol/mol), 45 acetaldehyde (1.7 nmol/mol), 47 formic acid (not quantified);59 acetone (2.9 nmol/mol), 61 acetic acid (not quantified), 63 dimethylsulphide (DMS) (289 pmol/mol), 69 isoprene (1.7 nmol/mol), 71 MVK + MACR (1.3nmol/mol), 73 methyl ethyl ketone (1.8 nmol/mol), 75 hydroxyacetone (606pmol/mol), 83 C₅ isoprene hydroxy carbonylsC₅H₈O₂, methyl furan, and cis 3-hexen-1-ol(732 pmol/mol), 87 C₅ carbonyls and methacrylic acid, 95 possibly2-vinyl furan (656 pmol/mol), 97 unknown (305 pmol/mol), 99 cis hexenal (512pmol/mol) and 101 isoprene C₅ hydroperoxides (575 pmol/mol). Somespecies agreed well with those derived from an isoprene only photochemicalmodel (e.g., mass 71 MVK + MACR) while others did not and were observed athigher than previously reported mixing ratios (e.g., mass 59 acetone, mass 63DMS). Monoterpenes were not detected above the detection limit of 300pmol/mol. Several species postulated are potentially important sources ofHO_x in the free troposphere, e.g., methanol, acetone, methyl ethylketone, methyl vinyl ketone and methacrolein.     

An Experimental Study on the Temperature Dependence for the Gas-Phase Reactions of NO3 Radical with a Series of Aliphatic Aldehydes

The absolute rate constants for the gas-phasereactions of the NO₃ radical with a series ofaldehydes such as acetaldehyde, propanal, butanal,pentanal, hexanal and, heptanal were measured overthe temperature range 298–433 K, using a dischargeflow system and monitoring the NO₃ radical byLaser Induced Fluorescence (LIF).The measured rate constants at 298 K for thereaction of NO₃, in units of 10^–14 cm³molecule^–1 s^–1, were as follows:acetaldehyde 0.32 ± 0.04, propanal 0.60 ± 0.06, butanal 1.46± 0.16, pentanal 1.75 ±0.06, hexanal 1.83 ± 0.36, and heptanal 2.37 ±0.42. The proposed Arrhenius expressions arek₁ = (6.2 ± 7.5) × 10^–11 exp[–(2826 ± 866)/T] (cm³ molecule^–1s^–1),k₂ = (1.7 ± 1.0) × 10^–11 exp[–(2250 ± 192)/T] (cm³ molecule^–1s¹), k₃ =(7.6 ± 9.8) × 10¹¹ exp[–(2466 ± 505)/T] (cm³ molecule^–1s^–1),k₄ = (2.8 ± 1.4) × 10^–11 exp[–(2189 ± 156)/T] (cm³ molecule^–1s^–1), k₅ = (7.0 ± 1.8) ×10^–11 exp [–(2382 ± 998)/T](cm³ molecule^–1 s^–1), andk₆ = (7.8 ± 1.0) × 10^–11 exp[–(2406 ± 481)/T](cm³ molecule^–1 s^–1).Tropospheric lifetimes for these aldehydes werecalculated at night and during the day for typicalNO₃ and OH average concentrations and showed thatboth radicals provide an effective tropospheric sinkfor these compounds and that the night-time reactionwith the NO₃ radical can be an important, if notdominant, loss process for these emitted organics andfor NO₃ radicals.     

Chemical Assessment of Oceanic and Terrestrial Sulfur in the Marine Boundary Layer over the Northern North Pacific during Summer

Dimethylsulfide (DMS) in surface seawater and the air, methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ²–) in aerosol, and radon-222 (Rn-222) were measured in the northern North Pacific, including the Bering Sea, during summer (13 July – 6 September 1997). The mean atmospheric DMS concentrations in the eastern region (21.0 ± 5.8 nmole/m³ (mean ± S.D.), n=30) and Bering Sea (19.9 ± 9.8 nmole/m³, n=10) were higher than that in the western region (11.1 ± 6.4 nmole/m³, n=31) (p<0.05), although these regions did not significantly differ in the mean DMS concentration in surface seawater. Mean sea-to-air DMS flux in the eastern region (21.0 ± 10.4 mole/m²/day, n=19) was larger than those in the western region (11.3 ± 16.9 mole /m²/day, n=22) and Bering Sea (11.2 ± 7.8 mole/m²/day, n=7) (p<0.05). This suggests that the longitudinal difference in atmospheric DMS was produced by that in DMS flux owing to wind speed, while the possible causes of the higher DMS concentrations in the Bering Sea include (1) later DMS oxidation rates, (2) lower heights of the marine boundary layer, and (3) more inactive convection. The mean MSA concentrations in the eastern region (1.18 ± 0.84 nmole/m³, n=35) and Bering Sea (1.17 ± 0.87 nmole/m³, n=13) were higher than that in the western region (0.49 ± 0.25 nmole/m³, n=28) (p < 0.05). Thus the distribution of MSA was similar to that of DMS, while the nss-SO₄ ²– concentrations were higher near the continent. This suggests that nss-SO₄ ²– concentrations were regionally influenced by anthropogenic sulfur input, because the distribution of nss-SO₄ ²– was similar to that of Rn-222 used as a tracer of continental air masses.     

Fourier transform infrared studies of the reaction of Cl atoms with PAN,PPN, CH3OOH,HCOOH, CH3COCH3 and CH3COC2H5 at 295±2 K

The relative rate technique has been used to measure rate constants for the reaction of chlorine atoms with peroxyacetylnitrate (PAN), peroxypropionylnitrate (PPN), methylhydroperoxide, formic acid, acetone and butanone. Decay rates of these organic species were measured relative to one or more of the following reference compounds; ethene, ethane, chloroethane, chloromethane, and methane. Using rate constants of 9.29×10^–11, 5.7×10^–11, 8.04×10^–12, 4.9×10^–13, and 1.0×10^–13 cm³ molecule^–1 sec^–1 for the reaction of Cl atoms with ethene, ethane, chloroethane, chloromethane, and methane respectively, the following rate constants were derived, in units of cm³ molecule^–1 s^–1: PAN, <7×10^–15; PPN, (1.14±0.12)×10^–12; HCOOH, (2.00±0.25)×10^–13; CH₃OOH, (5.70±0.23)×10^–11; CH₃COCH₃, (2.37±0.12)×10^–12; and CH₃COC₂H₅, (4.13±0.57)×10^–11. Quoted errors represent 2 and do not include possible systematic errors due to errors in the reference rate constants. Experiments were performed at 295±2 K and 700 torr total pressure of nitrogen or synthetic air. The results are discussed with respect to the previous literature data and to the modelling of nonmethane hydrocarbon oxidation in the atmosphere.In recent discussions with Dr. R. A. Cox of Harwell Laboratory, UKAEA, we learnt of a preliminary value for the rate constant of the reaction of Cl with acetone of (2.5±1.0)×10^–12 cm³ molecule^–1 sec^–1 measured by R. A. Cox, M. E. Jenkin, and G. D. Hayman using molecular modulation techniques. This value is in good agreement with our results.     

The role of clouds in tropospheric photochemistry

We show that photochemical processes in the lower half of the troposphere are strongly affected by the presence of liquid water clouds. Especially CH₂O, an important intermediate of CH₄ (and of other hydrocarbon) oxidation, is subject to enhanced breakdown in the aqueous phase. This reduces the formation of HO _x -radicals via photodissociation of CH₂O in the gas phase. In the droplets, the hydrated form of CH₂O, its oxidation product HCO₂ ^–, and H₂O₂ recycle O₂ ^– radicals which, in turn, react with ozone. We show that the latter reaction is a significant sink for O₃. Further O₃ concentrations are reduced as a result of decreased formation of O₃ during periods with clouds. Additionally, NO _x , which acts as a catalyst in the photochemical formation of O₃, is depleted by clouds during the night via scavenging of N₂O₅. This significantly reduces NO _x -concentrations during subsequent daylight hours, so that less NO _x is available for O₃ production. Clouds thus directly reduce the concentrations of O₃, CH₂O, NO _x , and HO _x . Indirectly, this also affects the budgets of other trace gases, such as H₂O₂, CO, and H₂.     

FTIR studies of reactions between the nitrate radical and haloethenes

Products and mechanisms for the gas-phase reactions of NO₃ radicals with CH₂=CHCl, CH₂=CCl₂, CHCl=CCl₂,cis-CHCl=CHCl andtrans-CHCl=CHCl in air have been studied. The experiments were carried out at 295±2 K and 740±5 Torr in a 480-L Teflon-coated reaction chamber and at 295±2 K and 760±5 Torr in a 250-L stainless steel reactor. NO₃ was generated by the thermal dissociation of N₂O₅. Experiments with¹⁵NO₃ and CD₂CDCl have also been performed. The initially formed nitrate peroxynitrates decay into carbonyl compounds, nitrates, HCl and ClNO₂. In adidtion, there are indications of nitrooxy acid chlorides being produced. The reactions with CH₂=CCl₂ and CHCl=CCl₂ are more complex due to release of chlorine atoms which eventually lead to formation of chloroacid chlorides.A general reaction mechanism is proposed and the observed concentration-time profiles of reactants and products are simulated for each compound. The rate constants for the initial step of NO₃ addition to the chloroethenes are determined as: (2.6±0.5, 9.4±0.9, 2.0±0.4 and 1.4±0.4) × 10^–16 cm³ molecule^–1 s^–1 for CH₂=CHCl, CH₂=CCl₂, CHCl=CCl₂ andcis-CHCl=CHCl, respectively.     

Oxidation of sulphur compounds in the atmosphere: I. Rate constants of OH radical reactions with sulphur dioxide,hydrogen sulphide,aliphatic thiols and thiophenol

The reactions of OH radicals with SO₂, H₂S, thiophenol, and a series of aliphatic thiols (1–5 C-atoms) have been investigated in 201 and 381 reaction chambers at 1 atm total pressure and 300 K using a competitive kinetic technique. Initially, OH radicals were produced by photolysis of CH₃ONO/NO mixtures in air. Applying this OH source rate constants for OH with SO₂, H₂S, and thiophenol in synthetic air were determined to be (1.1±0.2)×10^-12, (5.5±0.8)×10^-12 and (1.1±0.2)×10^-11 cm³ s^-1, respectively. However, when this method was applied to the aliphatic thiols the rate constants obtained were found to be dependent on the partial pressures of O₂ and NO. These effects have been attributed to the built-up of a radical species, not yet identified, which leads to uncontrolled chain reactions in the system. Using the photolysis of H₂O₂ at wavelengths greater than 260 nm as the OH source in 1 atm N₂, rate constants for the 1–5 aliphatic thiols in the range 2.9 to 5.6×10^-11 cm³ s^-1 were obtained. The rate constants obtained in the present study are compared with recent literature values.     

Carboxylic Acids: Seasonal Variation and Relation to Chemical and Meteorological Parameters

Formic and acetic acid measured as daily averages in 1993–1994show equal and highly correlated concentrations up to 3 ppb in the summer(May–August). In the winter (October–March) the formicacid/acetic acid ratio was 0.6 and the formic acid concentrations wereusually below 1 ppb. In winter the carboxylic acids correlate withO_x, NO_y, SO₂ and particulatesulphur. The main sources are suggested to be ozonolysis of anthropogenicalkenes and reactions between peroxyacetyl radicals and RO₂radicals. In spring–summer the carboxylic acids correlate withO₃, O_x, HNO₃, PAN,NO_y, SO₂, particulate sulphur and temperature.In addition to the sources of the winter a contribution from ozonolysis ofbiogenic alkenes is likely. Quite similar formic acid/acetic acid ratios forall wind directions suggest that the source(s) are atmospheric oxidationprocesses distributed over large areas. The highest concentrations occurringfor winds from east to south and the correlation with e.g., particulatesulphur indicate chemical production in polluted air masses during longrange transport.     

Mass transfer at the air/water interface: Mass accommodation coefficients of SO2, HNO3, NO2 and NH3

We present here experimental determinations of mass accommodation coefficients using a low pressure tube reactor in which monodispersed droplets, generated by a vibrating orifice, are brought into contact with known amounts of trace gases. The uptake of the gases and the accommodation coefficient are determined by chemical analysis of the aqueous phase.We report in this article measurements of _exp=(6.0±0.8)×10^–2 at 298 K and with a total pressure of 38 Torr for SO₂, (5.0±1.0)×10^–2 at 297 K and total pressure of 52 Torr for HNO₃, (1.5±0.6)×10^–3 at 298 K and total pressure of 50 Torr for NO₂, (2.4±1.0)×10^–2 at 290 K and total pressure of 70 Torr for NH₃.These values are corrected for mass transport limitations in the gas phase leading to =(1.3±0.1)×10^–1 (298 K) for SO₂, (1.1±0.1)×10^–1 (298 K) for HNO₃, (9.7±0.9)×10^–2 (290 K) for NH₃, (1.5±0.8)×10^–3 (298 K) for NO₂ but this last value should not be considered as the true value of for NO₂ because of possible chemical interferences.Results are discussed in terms of experimental conditions which determine the presence of limitations on the mass transport rates of gaseous species into an aqueous phase, which permits the correction of the experimental values.     

Rate constants for the reactions of the NO3 radical with HCOOH/HCOO− and CH3COOH/CH3COO− in aqueous solution between 278 and 328 K

The kinetics of the aqueous phase reactions of NO₃ radicals with HCOOH/HCOO^– and CH₃COOH/CH₃COO^– have been investigated using a laser photolysis/long-path laser absorption technique. NO₃ was produced via excimer laser photolysis of peroxodisulfate anions (S₂O ₈ ^2– ) at 351 nm followed by the reactions of sulfate radicals (SO ₄ ^– ) with excess nitrate. The time-resolved detection of NO₃ was achieved by long-path laser absorption at 632.8 nm. For the reactions of NO₃ with formic acid (1) and formate (2) rate coefficients ofk ₁=(3.3±1.0)×10⁵ l mol^–1 s^–1 andk ₂=(5.0±0.4)×10⁷ l mol^–1 s^–1 were found atT=298 K andI=0.19 mol/l. The following Arrhenius expressions were derived:k ₁(T)=(3.4±0.3)×10¹⁰ exp[–(3400±600)/T] l mol^–1 s^–1 andk ₂(T)=(8.2±0.8)×10¹⁰ exp[–(2200±700)/T] l mol^–1 s^–1. The rate coefficients for the reactions of NO₃ with acetic acid (3) and acetate (4) atT=298 K andI=0.19 mol/l were determined as:k ₃=(1.3±0.3)×10⁴ l mol^–1 s^–1 andk ₄=(2.3±0.4)×10⁶ l mol^–1 s^–1. The temperature dependences for these reactions are described by:k ₃(T)=(4.9±0.5)×10⁹ exp[–(3800±700)/T] l mol^–1 s^–1 andk ₄(T)=(1.0±0.2)×10¹² exp[–(3800±1200)/T] l mol^–1 s^–1. The differences in reactivity of the anions HCOO^– and CH₃COO^– compared to their corresponding acids HCOOH and CH₃COOH are explained by the higher reactivity of NO₃ in charge transfer processes compared to H atom abstraction. From a comparison of NO₃ reactions with various droplets constituents it is concluded that the reaction of NO₃ with HCOO^– may present a dominant loss reaction of NO₃ in atmospheric droplets.     

Rate constants for reactions of OH radicals with some Br-containing haloalkanes

Rate constants have been measured for the gas-phase reactions of hydroxyl radical with two halons and three of their proposed substitutes and also with CHClBr-CF₃ using the discharge-flow-EPR technique over the temperature range 298–460 K. The following Arrhenius expressions have been derived (units are 10^–13 cm³ molecule^–1 s^–1): (9.3 _–0.9 ^+1.0 ) exp{–(1326±33)/T} for CHF₂Br; (7.2 _–0.6 ^+0.7 ) exp{–(1111±32)/T} for CHFBrCF₃; (8.5 _–0.8 ^+0.9 ) exp{–(1113±35)/T} for CH₂BrCF₃; (12.8 _–1.2 ^+1.5 ) exp{–(995±38)/T} for CHClBrCF₃. The rate constants at 298 K have been estimated to be <2×10^–17 cm³ molecule^–1 s^–1 for CF₃Br and CF₂Br—CF₂Br. The atmospheric lifetimes due to hydroxyl attack have been estimated to be 5.5, 3.3, 2.8, and 1.2 years for CHF₂Br, CHFBr—CF₃, CH₂Br—CF₃ and CHClBr—CF₃, respectively.     

Nitrogen and sulfur species in Antarctic aerosols at Mawson,Palmer Station,and Marsh (King George Island)

High volume bulk aerosol samples were collected continuously at three Antarctic sites: Mawson (67.60° S, 62.50° E) from 20 February 1987 to 6 January 1992; Palmer Station (64.77° S, 64.06° W) from 3 April 1990 to 15 June 1991; and Marsh (62.18° S, 58.30° W) from 28 March 1990, to 1 May 1991. All samples were analyzed for Na⁺, SO ₄ ^2– , NO ₃ ^– , methanesulfonate (MSA), NH ₄ ⁺ ,²¹⁰Pb, and⁷Be. At Mawson for which we have a multiple year data set, the annual mean concentration of each species sometimes vary significantly from one year to the next: Na⁺, 68–151 ng m^–3; NO ₃ ^– , 25–30 ng m^–3; nss SO ₄ ^2– , 81–97 ng m^–3; MSA, 19–28 ng m^–3; NH ₄ ⁺ , 16–21 ng m^–3;²¹⁰Pb, 0.75–0.86 fCi m^–3. Results from multiple variable regression of non-sea-salt (nss) SO ₄ ^2– with MSA and NO ₃ ^– as the independent variables indicates that, at Mawson, the nss SO ₄ ^2– /MSA ratio resulting from the oxidation of dimethylsulfide (DMS) is 2.80±0.13, about 13% lower than our earlier estimate (3.22) that was based on 2.5 years of data. A similar analysis indicates that the ratio at Palmer is about 40% lower, 1.71±0.10, and more comparable to previous results over the southern oceans. These results when combined with previously published data suggest that the differences in the ratio may reflect a more rapid loss of MSA relative to nss SO ₄ ^2– during transport over Antarctica from the oceanic source region. The mean²¹⁰Pb concentrations at Palmer and Marsh and the mean NO ₃ ^– concentration at Palmer are about a factor of two lower than those at Mawson. The²¹⁰Pb distributions are consistent with a²¹⁰Pb minimum in the marine boundary layer in the region of 40°–60° S. These features and the similar seasonalities of NO ₃ ^– and²¹⁰Pb at Mawson support the conclusion that the primary source regions for NO ₃ ^– are continental. In contrast, the mean concentrations of MSA, nss SO ₄ ^2– , and NH ₄ ⁺ at Palmer are all higher than those at Mawson: MSA by a factor of 2; nss SO ₄ ^2– by 10%; and NH ₄ ⁺ by more than 50%. However, the factor differences exhibit substantial seasonal variability; the largest differences generally occur during the austral summer when the concentrations of most of the species are highest. NH ₄ ⁺ /(nss SO ₄ ^2– +MSA) equivalent ratios indicate that NH₃ neutralizes about 60% of the sulfur acids during December at both Mawson and Palmer, but only about 30% at Mawson during February and March.     

The Henry's Law Constants of the Haloacetic Acids

Henry's law constants K_H (mol kg^-1 atm^-1) have been measured between 278.15 K and 308.15 K for the following organic acids: CH₂FCOOH (ln(K_H[298.15 K]) = 11.3 ± 0.2), CH₂ClCOOH (11.59 ± 0.14), CH₂BrCOOH (11.94 ± 0.21), CHF₂COOH (10.32 ± 0.10), CHCl₂COOH (11.69 ± 0.11), CHBr₂COOH (12.33 ± 0.29), CBr₃COOH (12.61 ± 0.21), and CClF₂COOH (10.11 ± 0.12). The variation of K_H with temperature was determined for all acids except CH₂FCOOH and CBr₃COOH, with _r H° for the dissolution reaction ranging from –85.2 ± 2.6 to –57.1 ± 2.5 kJ mol^-1, meaning that their solubility is generally more sensitive to temperature than is the case for the simple carboxylic acids. The Henry's law constants show consistent trends with halogen substitution and, together with their high solubility compared to the parent (acetic) acid (ln(K_H[298.15 K]) = 8.61), present a severe test of current predictive models based upon molecular structure. The solubility of haloacetic acids and strong dissociation at normal pH mean that they will partition almost entirely into cloud and fog in the atmosphere (0.05–1.0 g H₂O m^-3), but can reside in both phases for the liquid water contents typical of aerosols (10^-5-10^-4 g H₂O m^-3).