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1.
The exchange of NO3 radicals with the aqueous-phase was investigated at room temperature (293 K) in a series of wetted denuders. From these experiments, the uptake coefficient of NO3 was determined on 0.1 M NaCl solutions and was found to be (NO3) 2 × 10-3 in good agreement with recent studies. The Henry coefficient of NO3 was estimated to be KH(NO3) = 1.8 M · atm-1, with a (2) uncertainty of ±3 M · atm-1. From the upper limit for the Henry coefficient (KH = 5 M · atm-1) and available thermodynamic data, the redox potential of dissolved NO3/NO 3 – is estimated to be in the range of 2.3 to 2.5 V. This range is at the lower boundary of earlier estimates. The results are discussed in the light of a recent publication. Based on our data and a model of the transport and chemistry in the liquid film, an upper limit is derived for the product of the Henry coefficient KH and the rate coefficient k 10 of the potential reaction NO3 + H2O HNO3 + OH. For KH = 0.6 M · atm-1, we find k 10 < 0.05 s-1 · atm-1, i.e., about 100 times smaller than what was suggested by Rudich and co-workers. Because of its small solubility, heterogeneous removal of NO3 is only important under conditions where the dissolved NO3 is removed quickly from equilibrium, for example by reactions with Cl– or HSO 3 – ions in the liquid-phase. Otherwise, heterogenous removal should mainly proceed via N2O5.  相似文献   

2.
Atmospheric nitric acid measurements by ACIMS (Active Chemical Ionization Mass Spectrometry) are based on ion-molecule reactions of CO3 -(H2O) n and NO3 -(H2O) n with HNO3. We have studied these reactions in the laboratory using a flow tube apparatus with mass spectrometric detection of reactant and product ions. Both product ion distributions and rate coefficients were measured. All reactions were investigated in an N2-buffer (1–3 hPa) at room temperature. The reaction rate coefficients of OH-, O2 -, O3 -, CO4 -, CO3 -, CO3 -H2O, NO3 -, and NO3 -H2O were measured relative to the known rate k=3.0×10-9 cm3 s-1 for the reaction of O- with HNO3. The main product ion of the reaction of CO3 -H2O with HNO3 was found to be (CO3HNO3)- supporting a previous suggestion made on the basis of balloon-borne ACIMS measurements. For the reaction of bare CO3 - with HNO3 three product ions were observed, namely NO3 -, (NO3OH)-, and (CO3HNO3)-. The reaction rate coefficients for CO3 -H2O (1.7×10-9 cm3 s-1) and NO3 -H2O (1.6×10-9 cm3 s-1) were found to be close to the collision rate. The measured k values for bare CO3 - (1.3×10-9 cm3 s-1) and NO3 - (0.7×10-9 cm3 s-1) are somewhat smaller. The collisional dissociations of CO3 -(H2O) n , NO3 -(H2O) n (n=1, 2), (CO3HNO3)- and (NO3HNO3)-, occasionally influencing ACIMS measurements, were also studied. Fragment ion distributions were measured using a triple quadrupole mass spectrometer. The results showed that previous stratospheric nitric acid measurements were unimpaired from collisional dissociation processes whereas these processes played a major role during previous tropospheric measurements leading to an underestimation of nitric acid concentrations. Previous ACIMS HNO3 detection was also affected by the conversion of CO3 -(H2O) n to NO3 -(H2O) n due to ion source-produced neutral radicals. A novel ACIMS ion source was developed in order to avoid these problems and to improve the ACIMS method.  相似文献   

3.
The results of an intercomparison campaign of eight different long path UV-visible DOAS instruments measuring NO2, O3 and SO2 concentrations in a moderately polluted urban site are presented. For effective optical path lengths of 230 and 780 m the overall spread of these measurements (±1) are 5×1010, 6×1010 and 1×1010 molec·cm-3 (2.0, 2.4, and 0.4 ppb) for these molecules respectively when all instruments used a common set of absorption cross sections. The remaining differences are not completely random and the systematic differences are attributed to the different retrieval methods used for each instrument.  相似文献   

4.
Tropospheric mercury is dominated by gas phase species. In this paper, the gas phase reactions between the nitrate radical and volatile biogenic mercury species have been investigated. An upper limit for the gas phase rate coefficient for reaction between elemental mercury and NO3-radicals was determined to 4 × 10–15 cm3 molecule–1 s–1 by using the fast flow-discharge technique. The reaction between dimethyl mercury and NO3, previously shown to be rapid, has also been studied in the laboratory with respect to product distribution using FT-IR. The result from the product study is consistent with a transformation of dimethyl mercury into inorganic, divalent mercury. All carbon delivered as dimethyl mercury was transformed into formaldehyde, methanol and methyl peroxynitrate. Hg was observed as a minor (2%) product. By exclusion, HgO is proposed as the mercury-containing product. Thus, the reaction between dimethyl mercury and the nitrate radical is excluded as a source of monomethyl mercury species in the atmosphere.  相似文献   

5.
A statistically relevant correlation between the reaction rate coefficient, k OH, for the OH radical reaction with 161 organic compounds in the gas phase at 300 K, and the corresponding vertical ionisation energies E i,v, reveals two classes of compounds: aromatics where –log(k OH/cm3s-1)3/2E i,v(eV)–2 and aliphatics where –log(k OH/cm3s-1)4/5E i,v(eV)+3. The prediction of the rate coefficient, k OH, for the reaction of OH with organic molecules from the above equations has a probability of about 90%. Assuming a global diurnal mean of the OH radical concentration of 5×105 cm3, the upper limit of the tropospheric half-life of organic compounds and their persistence can be estimated.  相似文献   

6.
The activation of Br- and Cl- to atomic Br and Cl in sea-spray aerosol was investigated in smog-chamber experiments. In the presence of O3, hydrocarbons and NaCl aerosol alone no activation was observed. By adding Br- to the aerosol, the chain reaction: Br + O3 BrO, BrO + HO2 HOBr, HOBr HOBr(aq), HOBr(aq) + H+ + Br- Br2 (6), HOBr(aq) + H+ + Cl- BrCl (7) was verified. The step from reaction (6) to (7) is accompanied by a decrease of the Br-/Cl- ratio from 1/600 to less than 1/2000. In the absence of sulphate, the chain is initiated by the reaction of OH(aq) with Br-. The pH value decreases to less than 2 during the first minutes of the experiment and later on to almost 1 (in the absence of NOx or SO2). This is caused by the formation of oxalic acid from alkanes and toluene. In stopped flow experiments, the reduction of Br2 by oxalic acid was observed to occur through a two-step mechanism: HC2O4 - + Br2 Br- + BrC2O4H (k22, k-22), BrC2O4H Br- + H+ + 2 CO2 (23) with the following rate constants and ratios of rate constants, k ± 2: k22k-23 / k-22 = (2.9 ± 0.3) · 10-4 s-1, k-22 / k-23 = 7000 ± 3000 13000 M-1, k22 = 2 ±-1 4 M-1 s-1, and k-23 > 0.1 s-1, k-22 > 600 M-1 s-1. Oxalic acid may be responsible for the inhibition of the chain reaction observed at the end of the experiments.  相似文献   

7.
A new version of an atmospheric pressure chemical ionisation mass spectrometer has been developed for ground based in situ atmospheric measurements of OH and total peroxy (HO2 + organic peroxy) radicals. Based on the previously developed principle of chemical conversion of OH radicals to H2SO4 in reaction with SO2 and detection of H2SO4 using an ion molecule reaction with NO3─, the new instrument is equipped with a turbulent chemical conversion reactor allowing for measurements in moderately polluted atmosphere at NO concentrations up to several ppb. Unlike other similar devices, where the primary NO3─ ions are produced using radioactive ion sources, the new instrument is equipped with a specially developed corona discharge ion source. According to laboratory measurements, the overall accuracy and detection limits are estimated to be, respectively, 25% and 2 × 105 molecule cm-3 for OH and 30% and 1 × 105 molecule cm-3 for HO2 at 10 min integration times. The detection limit for measurements of OH radicals under polluted conditions is 5 × 105 molecules cm-3 at 10 min integration times. Examples of ambient air measurements during a field campaign near Paris in July 2007 are presented demonstrating the capability of the new instrument, although with reduced performance due to the employment of non isotopic SO2.  相似文献   

8.
Using a filter radiometer, the meridional profile of the NO2 photolysis frequency, J(NO2), was measured between 50° N and 30° S during the cruise ANTVII/1 September/October 1988 of the research vessel Polarstern on the Atlantic Ocean. Simultaneously, global broadband irradiance and acrosol were monitored. Clean marine background air with low aerosol loads (b sp=(1–2)×10-5 m-1) was encountered at the latitudes 25° N–30° N and 18° S–27° S, respectively. Under these conditions and an almost cloudless sky J(NO2) reached 7.3×10-3 s-1 (2 sr) for a zenith angle of 30°. Between 30° N and 30° S, the latitudinal variation of the J(NO2) noontime maxima was less than ± 10%, while the mean value at noon was 7.8×10-3 s-1. For the set of all data between 50° N and 30° S, a nearly linear correlation of J(NO2) vs. global broadland irradiance was found. The slope of (8.24±0.03)×10-5 s-1/mW cm-2 agrees within 10% with observations in Jülich (51° N, 6.2° E).  相似文献   

9.
The reactivity of some selected biogenic monoterpenecompounds towards important aqueous phase free-radicaloxidants, namely OH· and SO4 -·, have beeninvestigated using the complementary experimentaltechniques of pulse radiolysis and laser flashphotolysis ( = 248 nm). Rate constants forthe reactions of the OH· radical with cis-verbenol andmethacrolein have been determined to be (6.8 ± 0.5) ×109 dm3 mol-1 s-1 and (8.0± 0.7) × 109 dm3 mol-1s-1,respectively (T = 20 °C, pH 4.0, Ionic strength 0 mol dm-3). Rate constants and activationenergies for the reactions of the SO4 -·radical have been measured for the following compounds(T = 20 °C, pH 4.0, Ionic strength = 0.03 moldm-3): -pinene (k = (3.1 ± 0.1) ×109 dm3 mol-1 s-1;E act. =(8.9 ± 1.3) kJ mol-1), -terpineol(k = (4.1 ± 0.1) × 109 dm3mol-1s-1; E act. = (13.4 ± 0.6) kJmol-1), cis-verbenol (k = (3.2 ± 0.2) ×109 dm3 mol-1 s-1;E act. =(10.0 ± 0.7) kJ mol-1), verbenone (k = (1.6± 0.1) × 109 dm3 mol-1s-1;E act. = (6.1 ± 0.7) kJ mol-1), myrtenal(k = (1.85 ± 0.1) × 109 dm3mol-1s-1; E act. = (7.5 ± 0.7) kJmol-1)and methacrolein (k = (1.18 ± 0.1) × 109dm3 mol-1 s-1). In most instances theabsorption spectra of the intermediate products formedby these reactions have been measured which, inconjunction with strategic conductiometric studies,have been used to suggest plausible mechanisms for theoxidation in acidic de-oxygenated solution.  相似文献   

10.
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.  相似文献   

11.
In the first two weeks of May 1981, the research jet of the German Aerospace Research Establishment (DFVLR) was charted to fly a meridional section between 5° and 82°N. A scanning filter photometer, developed at the Max Planck Institut für Aeronomie to measure column content values of atmospheric ozone and nitrogen dioxide, using ultra violet and visible absorption techniques, constituted part of the experimental payload for this campaign that was called SIMOC. The vertical NO2 column content above the aircraft, flying at approximately 10 km, was found to decrease rapidly from 6.9×1015 molecules cm-2 to 2.5×1015 molecules cm-2 around 50°N and then to increase again north of 75°N. A sharp rise in the NO2 content was observed south of the subtropical jet but this could possibly be due to the increased depth of the troposphere above the aircraft in these regions.  相似文献   

12.
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.  相似文献   

13.
A simple kinetic mechanism of nitrate radicals uptake on dry sea-salt NaCl, NaBr surfaces is proposed. The mechanism includes adsorption/desorption equilibrium and unimolecular decomposition of the adsorbed complex: NO3(g) + NaX(s) (NO3-NaX)(s); (NO3-NaX)(s) NaNO3 + X(s) Two techniques were used: the matrix isolation ESR and mass spectrometry. The uptake coefficient () is found to be dependent on exposure time of salt to NO3 for raw coating. The initial (t0) is higher than the observable steady-state obs. At room temperature obs is independent of [NO3] at low [NO3] = 3 × 109 - 1011 cm-3, but it is inversely proportional to [NO3] at concentrations higher than 1012 cm-3. At temperatures above 100 °C, obs becomes independent of [NO3] in a wider range of [NO3]. An increased number of dislocations is supposed to exist in the case of raw coating. Due to a wide spread of the surface sites binding energy with the ionic lattice near dislocations, the part of surface complexes has lower binding energy and "burns" more rapidly. That burning determines the transition from (t0) down to obs.The kinetic parameters and elementary rate coefficients are obtained. The recommended for low atmospheric NO3 concentration are in the range of 0.002 ± 0.04 for NaCl and 0.1-0.3 for NaBr depending on a mechanism of the (t) relaxation.  相似文献   

14.
Simultaneous measurements of peroxy and nitrate radicals at Schauinsland   总被引：3，自引：0，他引：3  
We present simultaneous field measurements of NO3 and peroxy radicals made at night in a forested area (Schauinsland, Black Forest, 48° N, 8° N, 1150 ASL), together with measurements of CO, O3, NO x , NO y , and hydrocarbons, as well as meteorological parameters. NO2, NO3, HO2, and (RO2) radicals are detected with matrix isolation/electron spin resonance (MIESR). NO3 and HO2 were found to be present in the range of 0–10 ppt, whilst organic peroxy radicals reached concentrations of 40 ppt. NO3, RO2, and HO2 exhibited strong variations, in contrast to the almost constant values of the longer lived trace gases. The data suggest anticorrelation between NO3 and RO2 radical concentrations at night.The measured trace gas set allows the calculation of NO3 and peroxy radical concentrations, using a chemical box model. From these simulations, it is concluded that the observed anthropogenic hydrocarbons are not sufficient to explain the observed RO2 concentrations. The chemical budget of both NO3 and RO2 radicals can be understood if emissions of monoterpenes are included. The measured HO2 can only be explained by the model, when NO concentrations at night of around 5 ppt are assumed to be present. The presence of HO2 radicals implies the presence of hydroxyl radicals at night in concentrations of up to 105 cm–3.  相似文献   

15.
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.  相似文献   

16.
The aqueous phase acid-catalyzed reaction of methanol (CH3OH) with nitric acid (HNO3) to yield methyl nitrate (CH3ONO2) under atmospheric conditions has been investigated using gas-phase infrared spectroscopy. Reactions were conducted in aqueous sulfuric acid solutions (50.5–63.6 wt.%) with [CH3OH] = 0.00005–0.005 M and [HNO3] = 0.02–0.21 M, at 278.2–328.6 K. Methyl nitrate production rates increased linearly with CH3OH and HNO3 concentrations and exponentially with sulfuric acid weight percent within the regime studied. Rates increased linearly with nitronium ion concentration, indicating that the reaction involves as the nitrating agent under these conditions. At 298 K, the rate of methyl nitrate production can be calculated from k obs [CH3OH][HNO3], where k obs  = 2.337 × 10−13(exp(0.3198*wt.% H2SO4)) when the solubility of CH3ONO2 in acidic solution is approximated by H* for pure water. The temperature dependence of the rate coefficient is related to solution composition, with activation energies of 59 and 49 kJ/mol at 51.1 and 63.6 wt.% H2SO4, respectively, when k is calculated from rate. The temperature dependence has also been parameterized for application to the atmosphere, but the small quantities of present in aerosol particles will result in methyl nitrate production rates too small to be of significance under most atmospheric conditions. An erratum to this article can be found at  相似文献   

17.
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.  相似文献   

18.
A discharge-flow tube coupled with resonance fluorescence and chemiluminescence detection has been used to investigate the reactions IO + HO2 products (1) and IO + O(3P) I + O2(2), at T = 296 ± 1 K and P = 1.7 - 2 Torr. The rate constants k-1 and k2 have been found to be (7.1 ± 1.6) × 10-11 cm3 molecule-1 s-1 and (1.35 ± 0.15) × 10-10 cm3 molecule-1 s-1, respectively.  相似文献   

19.
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.  相似文献   

20.
The design and performance of a smog chamber for the study of photochemical reactions under simulated environmental conditions is described. The chamber is thermostated for aerosol experiments, and it comprises a gas chromatographic sample enrichment system suitable for monitoring hydrocarbons at the ppbv level. By irradiating NO x /alkane-mixtures rate constants for the reaction of OH radicals with n-alkanes are determined from n-pentane to n-hexadecane to be (k±2)/10–12 cm3 s–1=4.29±0.16, 6.2±0.6, 7.52 (reference value), 8.8±0.3, 10.2±0.3, 11.7±0.4, 13.7±0.3, 15.1±0.5, 17.5±0.6, 19.3±0.7, 22.3±1.0, and 25.0±1.3, respectively at 312 K. Rate constants, (k±2)/10–17 cm3 s–1, for the reaction of ozone with trans-2-butene (21.2±1.0), cis-3-methylpentene-(2) (47.2±1.7), cyclopentene (62.4±3.5), cyclohexene (7.8±0.5), cycloheptene (28.3±1.5), -pinene (8.6±1.3), and -pinene (1.4±0.2) are determined in the dark at 297 K using cis-2-butene (13.0) as reference standard.  相似文献   

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