Nitric acid forming potential of five prototype hydrocarbons

The nitric acid formed from trans-2-butene, propene, ethene, toluene, and n-butane in single hydrocarbon/NO₂/purified air systems was examined in smog chamber experiments. The effect of hydrocarbon and NO₂ concentrations on the maximum HNO₃ yield, defined as percentages of initial NO₂ converted to HNO₃, was studied in two sets of experiments. In every hydrocarbon system, we found no effect of hydrocarbon concentration variation on the nitric acid formed. Out of initially added 100 ppb NO₂, in the hydrocarbon-rich systems, ethene formed most HNO₃ (45%), followed by propene, toluene, and n-butane (24%), and trans-2-butene (13%). When the initial NO₂ concentration was varied with a constant hydrocarbon concentration, the amount of HNO₃ formed was found to linearly increase with the added NO₂ down to |HC|/|NO₂| ratios, which depended on the nature of the hydrocarbon studied. The initial rate of HNO₃ formation in hydrocarbon excess experiments varied between 50, 35, 23, 16, and 8 ppb/hr for butene, propene, toluene, ethene, and butane systems, respectively.     

Products and mechanism of the reaction of NO3 with selected acyclic monoalkenes

The gas-phase reactions of NO₃ with 2-methyl-2-butene, isobutene,trans-butene, 1-butene and propene, were investigated in a flow-tube at room temperature. Experiments were performed in the pressure range 1–1000 mbar in synthetic air as well as at a total pressure of 800 mbar with varying concentrations of oxygen in nitrogen.The main products found were oxiranes, nitroxy-carbonyl compounds (ketonitrates) and ketones or aldehydes. The product distribution was a function of pressure. In each case, in synthetic air, the oxirane yield increased with decreasing total pressure up to a value of about 100% at pressures less than 1 mbar.It was concluded that oxirane is a product of the excited adduct radical formed in the electrophilic addition of NO₃ to the double bond. Experiments with very low partial pressures of oxygen showed that the quenched adduct radicals also produce the corresponding oxirane.Under tropospheric conditions (1000 mbar synthetic air) the following yields of the corresponding oxiranes were found: 2-methyl-2-butene 9%, isobutene 7%,trans-butene 12%, 1-butene 18%, propene 28%. In the case oftrans-butene the total oxirane yield consists of 72%trans- and 28%cis-isomer.Dedicated to Professor Wolfgang Rolle on the occasion of his 60th birthday.     

Urban Atmospheric Chemistry During the PUMA Campaign 2: Radical Budgets for OH,HO<Subscript>2</Subscript> and RO<Subscript>2</Subscript>

A detailed photochemical box model was used to investigate the key reaction pathways between OH, HO₂ and RO₂ radicals during the summer and winter PUMA field campaigns in the urban city-centre of Birmingham in the UK. The model employed the most recent version of the Master Chemical Mechanism and was constrained to 15-minute average measurements of long-lived species determined in situ at the site. The results showed that in the summer, OH initiation was dominated by the reactions of ozone with alkenes, nitrous acid (HONO) photolysis and the reaction of excited oxygen atoms atoms with water. In the winter, ozone+alkene reactions were the primary initiation route, with a minor contribution from HONO photolysis. Photolysis of aldehydes was the main initiation route for HO₂, in both summer and winter. RO₂ initiation was dominated by the photolysis of aldehydes in the summer with a smaller contribution from ozone+alkenes, a situation that was reversed in the winter. At night, ozone+alkene reactions were the main radical source. Termination, under all conditions, primarily involved reactions with NO (OH) and NO₂ (OH and RCO₃). These results demonstrate the importance of ozone+alkene reactions in urban atmospheres, particularly when photolysis reactions were less important during winter and at nighttime. The implications for urban atmospheric chemistry are discussed.     

Formation and occurrence of organic hydroperoxides in the troposphere: Laboratory and field observations

The formation and occurrence of hydroperoxides in the troposphere have been studied by laboratory experiments and by preliminary field measurements. Nine alkenes were reacted individually with ozone in a reaction chamber in the presence of excess water, and the amounts of hydrogen peroxide and of nine organic hydroperoxides produced in the gas and aerosol phases and deposited on the chamber walls determined by HPLC. The reactions of ethene, propene, 1-butene and isoprene gave hydroxymethyl hydroperoxide as the major product with no hydrogen peroxide observed. In the case of - and -pinene, 2-carene and limonene the major product was hydrogen peroxide. Cis-2-butene produced hydrogen peroxide and methyl hydroperoxide. Preliminary measurements of hydrogen peroxide and five organic hydroperoxides in ambient air were made at Niwot Ridge, Colorado from 24 July–4 August 1989. The gas-phase species were preconcentrated by cryotrapping with subsequent HPLC separation. The gas-phase concentrations of H₂O₂ ranged from 0.5–2 ppbv with the lowest concentrations being measured at night and the highest under conditions of strong photochemical activity. The maximum concentrations of hydroxymethyl hydroperoxide approximated those of H₂O₂. Methyl hydroperoxide concentrations ranged from <50 to 800 pptv and three other organic hydroperoxides were detected at concentrations below 200 pptv. High volume aerosol samples yielded H₂O₂ and methyl hydroperoxide concentrations <10 ng m^-3 while H₂O₂ and six organic species were detected in rainwater at concentrations in the range <0.01–50 M.     

Multi-Phase Chemistry of C<Subscript>2</Subscript> and C<Subscript>3</Subscript> Organic Compounds in the Marine Atmosphere

A box model is used to explore the detailed chemistry of C₂ and C₃ organic compounds in the marine troposphere by tracing the individual reaction paths resulting from the oxidation of ethane, ethene, acetylene, propane, propene and acetic acid. The mechanisms include chemical reactions in the gas phase and in the aqueous phase of clouds and aerosol particles at cloud level under conditions resembling those in the northern hemisphere. Organic hydroperoxides are found to be important intermediate products, with subsequent reactions leading partly to the formation of mixed hydroxy or carbonyl hydroperoxides that are readily absorbed into cloud water, where they contribute significantly to the formation of multifunctional organic compounds and organic acids. Organic hydroperoxides add little to the oxidation of sulfur dioxide dissolved in the aqueous phase, which is dominated by H₂O₂. Next to acetaldehyde and acetone, glycol aldehyde, glyoxal, methyl glyoxal and hydroxy propanone are prominent oxidation products in the gas and the aqueous phase. Acetaldehyde is not efficiently converted to acetic acid in clouds; the major local sources of acetic acid are gas-phase reactions. Other acids produced include hydroperoxy acetic, glycolic, glyoxylic, oxalic, pyruvic, and lactic acid. The mechanism of Schuchmann et al. (1985), which derives glycolic and glyoxylic acid from the oxidation of acetate, is found unimportant in the marine atmosphere. The principal precursors of glyoxylic acid are glyoxal and glycolic acid. The former derives mainly from acetylene and ethene, the latter from glycolaldehyde, also an oxidation product of ethene. The oxidation of glyoxylic acid leads to oxalic acid, which accumulates and is predicted to reach steady state concentrations in the range 30–90 ng m⁻³. This is greater, yet of the same magnitude, than the concentrations observed over the remote Pacific Ocean.     

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.     

Modelled and measured concentrations of peroxy radicals and nitrate radical in the U.S. Gulf Coast region during TexAQS 2006

Measurements of total peroxy radicals (HO₂?+?RO₂) and nitrate radical (NO₃) were made on the NOAA research vessel R/V?Brown along the U.S. Gulf Coast during the TexAQS 2006 field campaign. The measurements were modelled using a constrained box-model based upon the Master Chemical Mechanism (MCM). The agreement between modelled and measured HO₂?+?RO₂ was typically within ??40% and, in the unpolluted regions, within 30%. The analysis of the model results suggests that the MCM might underestimate the concentrations of some acyl peroxy radicals and other small peroxy radicals. The model underestimated the measurements of NO₃ by 60?C70%, possibly because of rapid heterogeneous uptake of N₂O₅. The MCM model results were used to estimate the composition of the peroxy radical pool and to quantify the role of DMS, isoprene and alkenes in the formation of RO₂ in the different regions. The measurements of HO₂?+?RO₂ and NO₃ were also used to calculate the gas-phase budget of NO₃ and quantify the importance of organic peroxy radicals as NO₃ sinks. RO₂ accounted, on average, for 12?C28% of the total gas-phase NO₃ losses in the unpolluted regions and for 1?C2% of the total gas-phase NO₃ losses in the polluted regions.     

Air pollutant emission rates and concentrations in medieval churches

A series of indoor air quality parameters were determined in two medieval churches, in Cyprus (temperature, relative humidity, total and UV solar radiation, CO₂ indoors and O₃, NO, NO₂ ^*, HNO₃ ^*, HCl, HCOOH, CH₃COOH indoors and outdoors). These data were used as input in a validated indoor air quality model to predict indoor air pollutant source strengths and species concentrations that resulted from dark or photochemical reactions. The NO and NO₂ emission rates due to the burning of incense or candles were estimated. Model results revealed that heterogeneous NO formation takes place simultaneously with the heterogeneous HONO formation. Also, model application has shown that indoor NO_x emissions resulted in decreased free radical concentrations, in contrast to the organic compound emissions, which increased free radical concentrations. This effect of indoor emissions on indoor radicals can partly explain the indoor enhancement/depression of indoor gaseous acid formation.     

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.     

A Chamber Investigation of Nitric Acid-Soot Aerosol Chemistry at 298 K

Long-pathlength infrared absorption spectroscopy wasused to investigate nitric acid-soot aerosol chemistryat 298 K and 0.5% relative humidity. Experimentswere performed by introducing nitric acid vapor(P_{HNO 3} 3 Pa, P_total 40 kPa) intoateflon-coated chamber and initiating acquisition ofinfrared spectra at 3 minute time intervals. After 36minutes of data collection, soot powder was rapidlyexpanded into nitric acid contained in the chamber togenerate a soot-HNO₃ aerosol. Infrared spectracollected before, and after, soot introduction to thechamber were used to characterize chamber wallreaction processes and soot aerosol chemistry,respectively. Three soot types were investigated(Degussa FW2, Cabot Monarch 1000, and crystallinegraphite), each yielding similar chemistry. Upon sootintroduction to the chamber both HNO₃ uptake andNO₂ production occurred, with the molar ratio ofHNO₃ uptake to NO₂ production varying from1.2 to 2.9 for the three soot types studied. Unreacted HNO₃ was present at the conclusion ofeach of the aerosol experiments, indicating incompleteconversion of HNO₃ into NO₂. Thisobservation suggested that `active' sites at the sootsurface responsible for the reduction of HNO₃ arenot regenerated (i.e., formed) in the reactionprocess. In essence, a titration occurred betweenthese active sites and HNO₃. The NO₂concentrations produced, the soot mass concentrationsused, and the BET measured specific surface area ofthe powders allowed computation of the surface densityof active sites of 4.0 × 10^-18 m²/active site(describing all three powders studied). This is thefirst reported measurement of surface density ofactive sites for nitric acid chemistry on soot. Sinceatmospheric heterogeneous reactions that exhibitsurface deactivation may, in principle, affect tracegas concentration, we perform an assessment in thisregard.     

Products and mechanisms of the gas phase reactions of NO3 with CH3SCH3, CD3SCD3, CH3SH and CH3SSCH3

Products and mechanisms of the reaction between the nitrate radical (NO₃) and three of the most abundant reduced organic sulphur compounds in the atmosphere (CH₃SCH₃, CH₃SH and CH₃SSCH₃), have been studied in a 480 L reaction chamber using in situ FT-IR and ion chromatography as analytical techniques. In the three reactions, methanesulphonic acid was found to be the most abundant sulphur containing product. In addition the stable products SO₂, H₂SO₄, CH₂O, and CH₃ONO₂ were identified and quantified and thionitric acid-S-methyl ester (CH₃SNO₂) was observed in the i.r. spectrum from all of the three reactions. Deuterated dimethylsulphide (CD₃SCD₃) showed an isotope effect on the reaction Deuterated dimethylsulphide (CD₃SCD₃) showed an isotope effect on the reaction rate constant (k_H/k_D) of 3.8±0.6, indicating that hydrogen abstraction is the first step in the NO₃+CH₃SCH₃ reaction, probably after the formation of an inital adduct.Based on the products and intermediates identified, reaction mechanisms are proposed for the three reactions.     

The influence of isoprene peroxy radical isomerization mechanisms on ozone simulation with the presence of NOx

Isoprene peroxy radical isomerizations (1,5- and 1,6-H shifts) have recently been proposed as important pathways regenerating and recycling HO_x (OH?+?HO₂) in the atmosphere under low-NO_x conditions (Peeters et al. Phys. Chem. Chem. Phys. 28: 5935?C5939 2009; da Silva et al. Environ. Sci. Technol. 44:250?C256 2010). Evaluation and comparison of the isoprene peroxy radical isomerization mechanisms from recent studies have been performed against isoprene-NO_x experiments conducted in the UNC dual outdoor smog chambers. Five different kinetic mechanisms were tested in this study, including the original Master Chemical Mechanism (MCM) v3.1; two modified MCM mechanisms both implementing isoprene peroxy radical isomerization reactions but with different rate coefficients; the Carbon Bond 6 (CB6) mechanism; and the ISO-UNC mechanism. Sensitivity analyses of the unsaturated hydroxyperoxy aldehydes (HPALDs) reaction mechanisms under fast isomerization have also been performed. The results indicate that the fast isomerization mechanism and the mechanisms with high OH yields from HPALDs photolysis both significantly enhance HO_x estimates with increasing isoprene/NO_x ratios. However, O₃ predictions, as well the isoprene decay rates are substantially overestimated. Our results suggest that given the current state of our knowledge, it is difficult to improve both HO_x levels and maintain reasonable O₃ simulations using the Peeters et al. (Peeters et al. Phys. Chem. Chem. Phys. 28: 5935?C5939 2009) mechanism.     

Laboratory measurements of the <Superscript>12</Superscript>C/<Superscript>13</Superscript>C kinetic isotope effects in the gas-phase reactions of unsaturated hydrocarbons with Cl atoms at 298 ± 3 K

The carbon kinetic isotope effects (KIEs) in the reactions of several unsaturated hydrocarbons with chlorine atoms were measured at room temperature and ambient pressure using gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS). All measured KIEs, defined as the ratio of the rate constants for the unlabeled and labeled hydrocarbon reaction k ₁₂/k ₁₃, are greater than unity or normal KIEs. The KIEs, reported in per mil according to ^Cl ɛ = (k ₁₂/k ₁₃−1) × 1000‰ with the number of experimental determinations in parenthesis, are as follows: ethene, 5.65 ± 0.34 (1); propene, 5.56 ± 0.18 (2); 1-butene, 5.93 ± 1.16 (1); 1-pentene, 4.86 ± 0.63 (1); cyclopentene, 3.75 ± 0.14 (1); toluene, 2.89 ± 0.31 (2); ethylbenzene, 2.17 ± 0.17 (2); o-xylene, 1.85 ± 0.54 (2). To our knowledge, these are the first reported KIE measurements for reactions of unsaturated NMHC with Cl atoms. Relative rate constants were determined concurrently to the KIE measurements. For the reactions of cyclopentene and ethylbenzene with Cl atoms, no rate constant has been reported in refereed literature. Our measured rate constants are: cyclopentene (7.32 ± 0.88) relative to propene (2.68 ± 0.32); ethylbenzene (1.15 ± 0.04) relative to o-xylene (1.35 ± 0.21), all × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹. The KIEs in reactions of aromatic hydrocarbons with Cl atoms are similar to previously reported KIEs in Cl-reactions of alkanes with the same numbers of carbon atoms. Unlike the KIEs for previously studied gas-phase hydrocarbon reactions, the KIEs for alkene–Cl reactions do not exhibit a simple inverse dependence on carbon number. This can be explained by competing contributions of normal and inverse isotope effects of individual steps in the reaction mechanism. Implications for the symmetries of the transition state structures in these reactions and the potential relevance of Cl-atom reactions on stable carbon isotope ratios of atmospheric NMHC are discussed.     

Acidity of Aerosols during Winter Heavy Haze Events in Beijing and Gucheng,China

We investigated the acidity and concentrations of water-soluble ions in PM_2.5 aerosol samples collected from an urban site in Beijing and a rural site in Gucheng, Hebei Province from November 2016 to January 2017 to gain an insight into the formation of secondary inorganic species. The average SO₄^2–, NO₃^–, and NH₄⁺ concentrations were 8.3, 12.5, and 14.1 μg m^–3, respectively, at the urban site and 14.0, 14.2, and 24.2 μg m^–3, respectively, at the rural site. The nitrogen and sulfur oxidation ratios in urban Beijing were correlated with relative humidity (with correlation coefficient r = 0.79 and 0.67, respectively) and the aerosol loadings. Based on a parameterization model, we found that the rate constant of the heterogeneous reactions for SO₂ on polluted days was about 10 times higher than that on clear days, suggesting that the heterogeneous reactions in the aerosol water played an essential role in haze events. The ISORROPIA II model was used to predict the aerosol pH, which had a mean (range) of 5.0 (4.9–5.2) and 5.3 (4.6–6.3) at the urban and rural site, respectively. Under the conditions with this predicted pH value, oxidation by dissolved NO₂ and the hydrolysis of N₂O₅ may be the major heterogeneous reactions forming SO₄^2– and NO₃^– in haze. We also analyzed the sensitivity of the aerosol pH to changes in the concentrations of SO₄^2–, NO₃^–, and NH₄⁺ under haze conditions. The aerosol pH was more sensitive to the SO₄^2– and NH₄⁺ concentrations with opposing trends, than to the NO₃^– concentrations. The sensitivity of the pH was relatively weak overall, which was attributed to the buffering effect of NH₃ partitioning.     

Laboratory spectroscopic studies of atmospherically important radicals using fourier transform spectroscopy

This paper describes laboratory experiments designed to obtain the infrared spectra of some atmospherically important radical species and related compounds. A Fourier transform spectrometer was used that was capable of yielding resolutions as great as 0.0024 cm^-1, and optical paths of up to 512 m were employed. The objective of the experiments was to obtain the spectra for subsequent application to remote sounding measurements in the atmosphere.Radicals were generated by a variety of chemical reactions involving atoms or other highly reactive precursors. Spectra of the ₃ band of NO₃, at ca. 1500 cm^-1, were obtained with up to 0.005 cm^-1 resolution using the reaction between NO₂ and O₃ to produce the radical. The most satisfactory source of ClO was found to be the reaction between Cl and O₃, and the (1-0) vibration-rotation band in the region 829–880 cm^-1 was recorded at a resolution of 0.02 cm^-1. We were unable to observe infrared absorption of HO₂ with any of the radical sources that we tested. High-resolution survey spectra were obtained of compounds used as reactants, or formed as side-products in the radical-generating processes. These compounds included N₂O₅, HNO₃, ClONO₂, FNO₂, Cl₂O, HO₂NO₂, and probably FO₂.The ability to monitor concentrations of the NO₃ radical in the visible region of the spectrum as well as the concentrations of reactants and other products in the infrared region allowed us to undertake a study of the time-dependent interactions occurring when NO₂ reacts with O₃. The results indicate the importance of heterogeneous processes, especially when traces of water are present, and lend credence to suggestions that heterogeneous mechanisms in the NO₃–N₂O₅–H₂O system might be a viable source of HNO₃ in the atmosphere.     

Fourier transform infrared kinetic studies of the reaction of HONO with HNO3, NO3 and N2O5 at 295 K

The kinetics of the reaction of nitrous acid (HONO) with nitric acid (HNO₃), nitrate radicals (NO₃) and dinitrogen pentoxide (N₂O₅) have been studied using Fourier transform infrared spectroscopy. Experiments were performed at 700 torr total pressure using synthetic air or argon as diluents. From the observed decay of HONO in the presence of HNO₃ a rate constant of k<7×10^-19 cm³ molecule^-1 s^-1 was derived for the reaction of HONO with HNO₃. From the observed decay of HONO in the presence of mixtures of N₂O₅ and NO₂ we have also derived upper limits for the rate constants of the reactions of HONO with NO₃ and N₂O₅ of 2×10^-15 and 7×10^-19 cm³ molecule^-1 s^-1, respectively. These results are discussed with respect to previous studies and to the atmospheric chemistry of HONO.     

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.     

Observations of nitric oxide fluxes over grass

Eddy correlation measurements of NO vertical flux were made periodically from October 1983 through June 1984 at a height of eight meters above grass in northeastern Illinois, U.S.A. From 207 data points, each representing a 25 min average, 19 daytime cases and 8 nighttime cases were selected on the basis of steady, nonadvective atmospheric conditions. Each case was represented by a set of data constituting a 3 to 5 hr average. Concentrations of O₃, NO, and NO _y (from which NO₂ was inferred) and local atmospheric and surface conditions also were measured, to provide the information necessary to assess the relative importance of surface deposition, surface emission, and air chemistry on the observed NO flux. On the basis of a linear regression analysis applied with independent variables representing physical, chemical, and biological processes, surface uptake of NO was very small for data primarily collected in the daytime during spring, and measured deposition velocities at a height of 8 m were very small, much smaller than expected for NO₂. For the same time period, the surface emission rates of elemental nitrogen in NO were in the range of 1.4 to 4.2 ng m^-2 s^-1 for moist, unsaturated soils at temperatures near 15° C. These emissions were partially masked in the measured fluxes by rapid in-air chemical reactions involving O₃ and NO₂. The effects of rapid in-air chemical reactions involving O₃ were to decrease the (upward) flux of NO with height. While the information collected at night was too limited to strongly support hypotheses concerning emissions and deposition, a pathway for NO production by reactions involving NO₃ and related compounds was indicated. For daytime conditions, this production pathway is not evident, probably because of the relatively strong effects of photochemical reactions involving NO, NO₂, and O₃.Formerly with the Chemical Technology Division of Argonne National Laboratory and currently affiliated with Bio-Rad Laboratories, Digilab Division, Minneapolis, MN, U.S.A.     

FT-IR Study of the Kinetics and Products of the Reactions of Dimethylsulphide, Dimethylsulphoxide and Dimethylsulphone with Br and BrO

Kinetics and products of the gas-phase reactions of dimethylsulphide (DMS), dimethylsulphoxide (DMSO) and dimethylsulphone (DMSO₂) with Br atoms and BrO radicals in air have beeninvestigated using on-line Fourier Transform Infrared Spectroscopy (FT-IR) as analytical technique at 740 ± 5 Torr total pressure and at 296 ± 3 K in a480 L reaction chamber. Using a relative rate method for determining the rate constants; the following values (expressed in cm³molecule^–1 s^–1) were found: k_DMS+Br = (4.9 ±1.0) ×10^–14, k_DMSO + Br < 6 × 10^–14,k_{DMSO 2} + Br 1 × 10^–15,k_DMSO + BrO = (1.0 ± 0.3) × 10^–14 andk_{DMSO 2} + BrO 3 × 10^–15 (allvalues are given with one on the experimental data). DMSO, SO₂, COS, CH₃SBr andCH₃SO₂Br were identified as the main sulphur containing products of the oxidation of DMS by Br atoms. From the reaction between DMSO and Br atoms, DMSO₂and CH₃SO₂Br were the only sulphur containing products thatwere identified. DMSO, DMSO₂ and SO₂ were identified as themain sulphur containing products of the reaction between DMS and BrO.DMSO₂ was found to be the only product of the reaction between DMSO and BrO. For the reactions of DMSO₂ with Br and BrO no products were identified because the reactions were too slow.The implications of these results for atmospheric chemistry are discussed.