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1.
Results from numerical investigations regarding the exchange of HNO3, NH3, and NH4NO3 between the atmosphere and the biosphere are presented. The investigations were performed with a modified inferential method which is based on the generally accepted micrometeorological ideas of the transfer of momentum, sensible heat and matter near the Earth's surface and the chemical reactions among these nitrogen compounds. This modified inferential method calculates the micrometeorological quantities (such as the friction velocity and the fluxes of sensible and latent heat), the height-invariant fluxes of the composed chemically conservative trace species with group concentrationsc 1=[HNO3]+[NH4NO3] (total nitrate),c 2=[NH3]+[NH4NO3] (total ammonia), andc 3=[HNO3]-[NH3] as well as the fluxes of the individual nitrogen compounds. The parameterization of the fluxes is based on the flux-gradient relationships in the turbulent region of the atmospheric surface layer. The modified inferential method requires only the data of wind velocity, temperature, humidity and concentrations (HNO3, NH3, and NH4NO3) measured at a reference height by stations of a monitoring network.  相似文献   

2.
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   

3.
This paper shows a comparative study of particle and surface ozone concentration measurements undertaken simultaneously at two distinct semi-urban locations distant by 4 km at Saint-Denis, the main city of La Réunion island (21.5° S, 55.5° E) during austral autumn (May 2000). Black carbon (BC) particles measured at La Réunion University, the first site situated in the suburbs of Saint-Denis, show straight-forward anti-correlation with ozone, especially during pollution peaks ( 650 ng/m3 and 15 ppbv, for BC and ozone respectively) and at night-time (90 ng/m3 and 18.5 ppbv, for BC and ozone respectively). NOx (NO and NO2) and PM10 particles were also measured in parallel with ozone at Lislet Geoffroy college, a second site situated closer to the city centre. NOx and PM10 particles are anti-correlated with ozone, with noticeable ozone destruction during peak hours (mean 6 and 9 ppbv at 7 a.m. and 8 p.m. respectively) when NOx and PM10 concentrations exhibit maximum values. We observe a net daytime ozone creation (19 ppbv, O3 +4.5 ppbv), following both photochemical and dynamical processes. At night-time however, ozone recovers (mean 11 ppbv) when anthropogenic activities are lower ([BC] 100 ng/m3). BC and PM10 concentration variation obtained during an experiment at the second site shows that the main origin of particles is anthropogenic emission (vehicles), which in turn influences directly ozone variability. Saint-Denis BC and ozone concentrations are also compared to measurements obtained during early autumn (March 2000) at Sainte-Rose (third site), a quite remote oceanic location. Contrarily to Saint-Denis observations, a net daytime ozone loss (14.5 ppbv at 4 p.m.) is noticed at Sainte-Rose while ozone recovers (17 ppbv) at night-time, with however a lower amplitude than at Saint-Denis. Preliminary results presented here are handful data sets for modelling and which may contribute to a better comprehension of ozone variability in relatively polluted areas.  相似文献   

4.
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   

5.
Tropospheric photodissociation rate coefficients (J values) were calculated for NO2, O3, HNO2, CH2O, and CH3CHO using high spectral resolution (0.1 mm wavelength increments), and compared to the J values obtained with numerically degraded resolution (=1, 2, 4, 6, 8, and 10 nm, and several commonly used nonuniform grids). Depending on the molecule, substantial errors can be introduced by the larger increments. Thus for =10 nm, errors are less than 1% for NO2, less than 2% for HNO2, +6.5% to -16% for CH2O, -6.9% to +24% for CH3CHO, and -24% to +110% for O3. The errors for CH2O arise from the fine structure of its absorption spectrum, and are prevalently negative (underestimate of J). The errors for O3, and to a lesser extent for CH3CHO, arise mainly from under-resolving the overlap of the molecular action spectrum and the tropospheric actinic flux in the wavelength region of stratospheric ozone attenuation. The sign of those errors depends on whether the actinic flux is averaged onto the grid before or after the radiative transfer calculation. In all cases studied, grids with 2 nm produced errors no larger than 5%.  相似文献   

6.
The kinetics and mechanism of the reactionNO3+CH2=C(CH3)–CH=CH2productswere studied in two laboratories at 298 K in the pressure range 0.7–3 torr using the discharge-flow mass-spectrometric method. The rate constant obtained under pseudo-first-order conditions with excess of either NO3 or isoprene was: k 1=(7.8±0.6)×10–13 cm3 molecule–1 s–1. The product analysis indicated that the primary addition of NO3 occurred on both -bonds of the isprene molecule.  相似文献   

7.
A liquid jet of 90 m diameter and variable length has been utilized to determine absorption rates and, hence, mass accommodation coefficients , of atmospheric trace gases. The compounds investigated are HCl (0.01), HNO3 (0.01), N2O5 (0.005), peroxyacetyl nitrate (>0.001), and HONO (0.005). It is concluded that the absorption of these trace gases by liquid atmospheric water is not significantly retarded by interfacial mass transport. The strengths and limitations of the liquid jet technique for measuring mass accommodation coefficients are explored.  相似文献   

8.
Upto 13% of -pinene and 3-carene had reacted after 213 s in this dark experimental set-up, where O3, NO and NO2 were mixed with terpenes at different relative humidities (RHs). The different experiments were planned according to an experimental design, where O3, NO2, NO, RH and reaction time were varied between high and low settings (25 and 75 ppb, 15 and 42%, 44 and 213 s). An increased amount of -pinene and 3-carene reacted in the chamber was observed, when the level of O3, NO and reaction time was increased and RH was decreased. In the study, it was found that different interactions affected the amount of terpene reacted as well. These interactions were between O3 and NO, O3 and reaction time, NO and RH, and between NO and reaction time.  相似文献   

9.
The NO3 radical initiated oxidation of cyclopentene, cyclohexene and 1-methyl-cyclohexene has been studied. The products formed in an N2O5-NO2-N2-O2-cycloalkene-static reactor system, at 0.1 MPa and 296 K, were investigated using long path FTIR. The principal products were aldehydes formed via a ring opening process. The reactions also resulted in significant yields of three types of ring retaining nitrooxy-substituted compounds. The average yields of alkyl nitrates from, e.g., reactions with cycloalkene were 25.1% 2-oxo-cyclohexyl nitrate, 22.8% 2-hydroxy-cyclohexyl nitrate and 4.0% 1,2-cyclohexyl dinitrate. The mechanisms involved resembles those proposed for acyclic alkenes. In absence of NO, -oxo and -hydroxy-cycloalkyl nitrates are formed via self reactions of -nitrooxy substituted cycloalkyl peroxy radicals. Estimated branching ratios for the reactants leading to ring retaining products in the presence and in the absence of NO are given and the possible relevance of these reactions for cycloalkenes under tropospheric conditions is discussed.  相似文献   

10.
The reactions of alkoxy radicals determine to a large extent the products formed during the atmospheric degradations of emitted organic compounds. Experimental data concerning the decompositions, 1,5-H shift isomerizations and reactions with O2 of several classes of alkoxy radicals are inconsistent with literature estimations of their absolute or relative rate constants. An alternative, although empirical, method for assessing the relative importance under atmospheric conditions of the reactions of alkoxy radicals with O2 versus decomposition was derived. This estimation method utilizes the differences in the heats of reaction, (H)=(Hdecomposition–HO 2 reaction), between these two reactions pathways. For (H)[22–0.5(HO 2 reaction)], alkoxy radical decomposition dominates over the reaction with O2 at room temperature and atmospheric pressure of air, while for (H)[25-0.5(HO 2 reaction)], the O2 reaction dominates over decomposition (where the units of H are in kcal mol–1). The utility and shortcomings of this approach are discussed. It is concluded that further studies concerning the reactions of alkoxy radicals are needed.  相似文献   

11.
The photooxidation of -humulene in the presence of NOx, natural sunlight, and rural background air was investigated using a combination of gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC). Identification and quantification of gas and particulate reaction products were reported over the course of the reaction. The daytime photooxidation was carried out in a large outdoor smog chamber (190 m3). A wide range of ring retaining and ring opening products in the gas and particle phase are reported. On average, measured gas and particle phase products accounted for 44% of the reacted -humulene carbon. Measurements show that a number of reaction products with low vapor pressures (e.g. 3-seco--humulone aldehyde, 7-seco--humulone aldehyde, -humulal aldehyde, -humulene 3-oxide or -humulene 7-oxide, -humulaic/alic acid isomers, and 3-seco--14-hydroxyhumulone aldehyde) were found in the early stage of the reaction and may play an important role in the early formation of secondary organic aerosol. A detailed mechanism is proposed to account for most products observed in this investigation.  相似文献   

12.
Weekly bulk aerosol samples collected at Funafuti, Tuvalu (8°30S, 179°12E), American Samoa (14°15S, 170°35W), and Rarotonga (21°15S, 159°45W), from 1983 through most of 1987 have been analyzed for nitrate and other constituents. The mean nitrate concentration is about 0.11 g m–3 at each of these stations: 0.107±0.011 g m–3 at Funafuti; 0.116±0.008 at American Samoa; and 0.117±0.010 at Rarotonga. Previous measurements of mineral aerosol and trace metal concentrations at American Samoa are among the lowest ever recorded for the near-surface troposphere and indicate that this region is minimally affected by transport of soil material and pollutants from the continents. Consequently, the nitrate concentration of 0.11 g m–3 can be regarded as the natural level for the remote marine boundary layer of the tropical South Pacific Ocean. In contrast, over the tropical North Pacific which is significantly impacted by the transport of material from Asia and North America, the mean nitrate concentrations are about three times higher, 0.29 and 0.36 g m–3 at Midway and Oahu, respectively. The major sources of the nitrate over the tropical South Pacific are still very uncertain. A very significant correlation between the nitrate concentrations at American Samoa and the concentrations of 210Pb suggests that transport from continental sources might be important. This continental source could be lightning, which occurs most frequently over the tropical continents. A near-zero correlation with 7Be indicates that the stratosphere and upper troposphere are probably not the major sources. A significant biogenic source would be consistent with the higher mean nitrate concentrations, 0.16 to 0.17 g m–3, found over the equatorial Pacific at Fanning Island (3°55N, 159°20W) and Nauru (0°32S, 166°57E). The lack of correlation between nitrate and nss sulfate at American Samoa does not necessarily preclude an important role for marine biogenic sources.  相似文献   

13.
The yields of products have been calculated for the reactions of hydroxyl radicals and ozone with 19 of the two-through-six carbon anthropogenic alkenes. Based on their rate of reaction, mechanisms of reactions and the ambient air distribution for these alkenes their seasonal ambient air yields have been estimated.Aldehydes predominate as products irrespective of season, with smaller yields of several ketones. Other minor products include carboxylic acids, carbon monoxide, carbon dioxide, and alkenes. About a two-fold increase is estimated in the yields of hot biradicals and their products from summer to winter.One sensitivity analysis was made by recomputing yields at a different OH radical to O3 concentration than assumed most likely in the calculations discussed above. In addition, the sensitivity of product yields to an estimated range of seasonally averaged sunset-to-sunrise NO3 radical concentrations was calculated. The effects of free radical reactions are discussed, but these are believed to make a relatively minor contribution within the NO x -rich atmospheres that contain anthropogenic alkenes.The uncertainties in product yields associated with the range of NO3 radical concentrations assumed present is relatively small for aldehydes, as is the decrease in yield of the one carbon hot biradical. Larger uncertainties occur for ketones. Significant decreases in yields occur for larger hot biradicals, especially the branched-chain hot radicals in the presence of NO3 radicals.  相似文献   

14.
The formation yields of nine carbonyl products are reported from the gas-phase OH radical-initiated reactions (in the presence of NO x ) and the O3 reactions with seven monoterpenes. The products were identified using GC/MS and GC-FTIR and quantified by GC-FID analyses of samples collected on Tenax solid adsorbent cartridges. The identities of products from camphene, limonene and -pinene were confirmed by comparison with authentic standards. Sufficient quantities of products from the 3-carene, limonene, -pinene, sabinene and terpinolene reactions were isolated to allow structural confirmation by proton NMR spectroscopy. The measured total carbonyl formation yields ranged from non-detectable for the OH radical reaction with camphene and the O3 reactions with 3-carene and limonene to 0.5 for the OH radical reaction with limonene and the O3 reaction with sabinene.  相似文献   

15.
The gas and particle phase reaction products of a mixture of the atmospherically important terpenes -pinene and -pinene with the atmospheric oxidants O3 and OH/NOx were investigated using both gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC) for identification and quantification of reaction products. The nighttime oxidation of a mixture of -pinene and -pinene in the presence of O3/air, and the daytime oxidation of a mixture of -pinene + -pinene with NOx air in the presence of natural sunlight were carried out in the University of North Carolina's large outdoor smog chamber (190 m3) located in Chatham County, North Carolina. Mass balances for gaseous and aerosol reaction products are reported over the course of the reaction. More than twenty-nine products were identified and/or quantified in this study. On average, measured gas and particle phase products accounted for 74 to 80% of the reacted -pinen/-pinene mixture carbon. Measurements show that a number of reaction products were found in both O3 and NOx system [pinonaldehyde, pinic acid, pinonic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, 4-oxonopinone, 1-hydroxy-nopinone, 3-hydroxy-nopinone, and nopinone]. Pinonic acid, pinic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, and 10-hydroxypinonic acid were observed in the early stage in the aerosol phase and may play an important role in the early formation of secondary aerosols.  相似文献   

16.
The spatial variability of turbulent flow statistics in the roughness sublayer (RSL) of a uniform even-aged 14 m (= h) tall loblolly pine forest was investigated experimentally. Using seven existing walkup towers at this stand, high frequency velocity, temperature, water vapour and carbon dioxide concentrations were measured at 15.5 m above the ground surface from October 6 to 10 in 1997. These seven towers were separated by at least 100m from each other. The objective of this study was to examine whether single tower turbulence statistics measurements represent the flow properties of RSL turbulence above a uniform even-aged managed loblolly pine forest as a best-case scenario for natural forested ecosystems. From the intensive space-time series measurements, it was demonstrated that standard deviations of longitudinal and vertical velocities (u, w) and temperature (T) are more planar homogeneous than their vertical flux of momentum (u* 2) and sensible heat (H) counterparts. Also, the measured H is more horizontally homogeneous when compared to fluxes of other scalar entities such as CO2 and water vapour. While the spatial variability in fluxes was significant (>15 %), this unique data set confirmed that single tower measurements represent the canonical structure of single-point RSL turbulence statistics, especially flux-variance relationships. Implications to extending the moving-equilibrium hypothesis for RSL flows are discussed. The spatial variability in all RSL flow variables was not constant in time and varied strongly with spatially averaged friction velocity u*, especially when u* was small. It is shown that flow properties derived from two-point temporal statistics such as correlation functions are more sensitive to local variability in leaf area density when compared to single point flow statistics. Specifically, that the local relationship between the reciprocal of the vertical velocity integral time scale (Iw) and the arrival frequency of organized structures (/h) predicted from a mixing-layer theory exhibited dependence on the local leaf area index. The broader implications of these findings to the measurement and modelling of RSL flows are also discussed.  相似文献   

17.
The study focuses on a way to parameterize the effect of subgrid scale convective motions on surface fluxes in large scale and regional models for the case of light surface winds. As previously proposed, these subgrid effects are assumed to scale with the convection intensity through the relationship: where is the mean velocity of the wind, U0 the velocity of the mean wind, w* the free convection velocity, and an empirical coefficient to be determined. Both observations and numerical simulation are presently used to determine the free convection coefficient .Large eddy simulation of a fair weather convective boundary layer case observed during TOGA-COARE is performed. Comparisons between observations and the simulation of surface properties and vertical profiles in the planetary boundary layer are presented. The simulated vertical turbulent fluxes of heat, moisture and buoyancy range well within estimates from aircraft measurements.The most important result is that the true free convection coefficient , directly estimated from simulation, leads to a value of 0.65, smaller than the ones estimated from temporal and spatial variances. Using observations and simulation, estimates of from temporal and spatial variances are obtained with similar values 0.8. From both theoretical derivations and numerical computations, it is shown that estimates of the true from variances are possible but only after applying a correction factor equal to 0.8. If this correction is not used, is overestimated by about 25%. The time and space sampling problem is also addressed in using numerical simulations.  相似文献   

18.
STAR (System for Transfer of Atmospheric Radiation) was developed to calculate accurately and efficiently the irradiance, the actinic flux, and the radiance in the troposphere. Additionally a very efficient calculation scheme to computer photolysis frequencies for 21 different gases was evolved. STAR includes representative data bases for atmospheric constituents, especially aerosol particles. With this model package a sensitivity study of the influence of different parameter on photolysis frequencies in particular of O3 to Singlet D oxygen atoms, of NO2, and of HCHO was performed. The results show the quantitative effects of the influence of the solar zenith angle, the ozone concentration and vertical profile, the aerosol particles, the surface albedo, the temperature, the pressure, the concentration of NO2, and different types of clouds on the photolysis frequencies.Notation I A(, ) actinic flux - I H(, ) irradiance - L(, , , ) radiance - wavelength - azimuth angle - cosine of zenith angle - s cosine of solar zenith angle - optical depth - s scattering coefficient - c extinction coefficient - o single scattering albedo - p mix mixed phase function - g mix mixed asymmetry factor - J gas photolysis frequency  相似文献   

19.
On the Significance of the Webb Correction to Fluxes   总被引：2，自引：0，他引：2  
For establishing correct mass or energy balances at the Earth's surface, detailed and correct measurements of air constituent fluxes are needed. Flux measurements obtained from the eddy covariance technique have to pass several corrections of different relevance in order to give correct flux data. One of these corrections, the Webb correction, is analysed herein from latent heat flux and CO2 flux data recorded during two field experiments. The significance of this correction for the latent heat flux data varies with the air humidity and the Bowen ratio. The correction changes the latent heat flux values only a little, but significantly (by 2 to 3%). For other air constituents (like CO2), the Webb correction is much more important (20 to 30% of the flux).  相似文献   

20.
When applied to a sea surface, shortcomings are noted for the ordinary classification of drag conditions at rigid underlying surfaces according to the Reynolds roughness number Re s . It is shown that in the case of mobile underlying surfaces, it would be more natural to use the dynamical classification of drag conditions according to the order of magnitude of the ratio ( = /) of the momentum flux toward the waves ( w) to the viscous momentum flux through the surface ( w). The relevant estimates of for the main stages of development of the wind waves indicate that the observed values of the drag coefficient of the sea surface correspond to the case of underdeveloped roughness.  相似文献   

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