Gas and Particulate Products Distribution from the Photooxidation of α-Humulene in the Presence of NOx, Natural Atmospheric Air and Sunlight

The photooxidation of -humulene in the presence of NO_x, 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.     

Determination of carbon balances for smog chamber terpene oxidation experiments using a 14C tracer technique

In the last decade, numerous studies of monoterpene hydrocarbons in the presence of ozone and oxides of nitrogen have been completed. Although insights about the reactivity of terpenes have been gained, and several products have been identified in the gas and aerosol phases, carbon balances have been generally poor. This paper describes a radiotracer technique which accounts for carbon-containing compounds in a smog chamber at the conclusion of a photooxidation or ozonolysis reaction. Instead of attempting to identify individual products, gas-phase compounds were separated from aerosols, and each phase was analyzed by a liquid scintillation counter. A carbon balance of 79 to 97% was obtained with ¹⁴C--pinene and ozone using this technique. The significance of the results are discussed in terms of the ¹⁴C--pinene concentrations used in this study, which were lower than concentrations used previously by one to four orders of magnitude. In spite of the lower concentrations, the gaseous and aerosol fractions observed in the present investigation are comparable to those observed by others. Possible reaction products are discussed with respect to likely mechanisms for -pinene oxidation.     

The behaviour of aerosol optical depth during clear summer days in Athens,Greece

Summary The integral aerosol optical depths (k ) at the hour of 08:20 Local Standard Time (LST), are compared with those calculated previously at 11:20 and 14:20 LST, for clear days during summer in Athens over the period 1962–1988. The mean values at 08:20 LST were consistently lower than the values at 11:20 and 14:20 LST. The influence of the vertical wind profile on the values ofk was also investigated. A comparison was made of the wind profiles at 02:00 and 14:00 LST, for days in which the 11:20 and 14:20 LST values ofk were 0.200 andk 0.350, respectively. The corresponding bulk wind shear s was also found for the period 1980–1988. The most significant results occurred with the first category of days. The resultant wind velocities from the surface to the 900 hPa level, in each hour were higher by 2–4 m·s^–1 with respect to the corresponding values for the second category. At 02:00 LST the bulk wind shear showed a considerable difference (1.8) between the two categories of days in the surface to 700 hPa layer at 02:00 LST. Finally, the associated weather conditions that appear to initiate a period of low values ofk (k 0.200) at 11:20 and 14:20 LST were examined for the period 1980–1988. Fifteen such cases were identified and it was found that they all occurred after the passage of weak cold fronts.With 6 Figures     

Free convection frequency spectra of atmospheric turbulence over the sea

Frequency spectra of atmospheric turbulenceS (f) in the inertial subrange are considered in the free convection regime over the sea surface in a case of motionless instrument measurements (Eulerian frequency spectra). The frequency spectra formulaef _* S (f)/ ² =c (f _*/f)^5/3 for wind velocity (=1–3), temperature (=t) and humidity (=e) fluctuations are derived on the basis of similarity theory and the –5/3 law. These relations also can be derived from a consideration of convective large-scale advection of small eddies. The frequency scalef _* = (N ^{1 2}/)^1/2 (H/z ²)^1/3 is the lower bound of the inertial subrange and it is of order 10^–2 Hz.The spectra formulae are compared with direct measurements of atmospheric turbulence from the fixed research tower in the coastal zone of the Black Sea in calm weather. It is shown that these formulae are realized at least over two to three decades of the frequency range (approximately from 10^–2 to 10 Hz) and values of the numerical coefficients are found. The derived formulae can be used for calculations of sensible and latent heat fluxes by measuring the high-frequency range of spectra at a fixed point at low wind speeds when the conventional inertial dissipation method is not applicable.     

Drag and drag partition on rough surfaces

An analytic treatment of drag and drag partition on rough surfaces is given. The aims are to provide simple predictive expressions for practical applications, and to rationalize existing laboratory and atmospheric data into a single framework. Using dimensional analysis and two physical hypotheses, theoretical predictions are developed for total stress (described by the square root of the canopy drag coefficient), stress partition (described by the ratio _S/ of the stress _s on the underlying ground surface to total stress ), zero-plane displacement and roughness length. The stress partition prediction is the simple equation _S/= 1/(1+), where = C_RC_S the ratio of element and surface drag coefficients. This prediction agrees very well with data and is free of adjustable constants. Other predictions also agree well with a range of laboratory and atmospheric data.     

The validation of various schemes for parameterizing evaporation from bare soil for use in meteorological models: A numerical study using in situ data

Parameterization of evaporation from a non-plant-covered surface is very important in the hierarchy strategy of modelling land surface processes. One of the representations frequently used in its computation is the resistance formulation. The performance of the evaporation schemes using the , , and their combination resistance approaches to parameterize evaporation from bare soil surfaces is discussed. For that purpose, the nine schemes, based on a different dependence of and on volumetric soil moisture content and its saturated value, are used.The tests of performances of the considered schemes are based on time integrations by the land surface module (BARESOIL) using observed data. The 23 data sets at a bare surface experimental site in Rimski anevi, Yugoslavia on chernozem soil, were used for the resistance algorithm evaluation. The quality of the schemes was compared with the observed values of the latent heat flux using several statistical parameters.     

Gas-Phase Ozone Oxidation of Monoterpenes: Gaseous and Particulate Products

Atmospheric oxidation of monoterpenes contributes to formation of tropospheric ozone and secondary organic aerosol, but their products are poorly characterized. In this work, we report a series of outdoor smog chamber experiments to investigate both gaseous and particulate products in the ozone oxidation of four monoterpenes: -pinene, -pinene, ³-carene, and sabinene. More than ten oxygenated products are detected and identified in each monoterpene/O₃ reaction by coupling derivatization techniques and GC/MS detection. A denuder/filter pack sampling system is used to separate and simultaneously collect gas and aerosol samples. The identified products, consisting of compounds containing carbonyl, hydroxyl, and carboxyl functional groups, are estimated to account for about 34–50%, 57%, 29–67%, and 24% of the reacted carbon mass for -pinene, sabinene, -pinene, and ³-carene, respectively. The identified individual products account for >83%, 100%, >90%, and 61% of the aerosol mass produced in the ozone reaction of -pinene, sabinene, -pinene, and ³-carene. The uncertainty in the yield data is estimated to be ±50%. Many of the products partition between gas and aerosol phases, and their gas-aerosol partitioning coefficients are determined and reported here. Reaction schemes are suggested to account for the products observed.     

Analytical investigations of horizontal meso-scale momentum equations with Newtonian nudging

Summary This study presents an analytical investigation of the local behaviour of the solution to a mesoscale model with Newtonian nudging when observed winds are time varying. The analysis examines each Fourier component of the time series of observed winds. Unlike the case with a constant observed wind, the nudged wind vector does not asymptotically approach the observed wind. In response to sinusoidal oscillation of the observed wind, the nudged wind vector is always on a half circle connecting the vector ends of the observed and un-nudged modelled winds. When nudging parameter 0, the nudged wind vector approaches the un-nudged wind; when , the nudged wind vector approaches the observed wind. For commonly used values of nudging parameter , the modelled wind field always carries errors.A target nudging scheme is devised in this study in order to ensure the model result is identical to observed winds with sinusoidal oscillation. Investigation shows that such a target wind exists for a finite value of , and the magnitude of the target-nudging term is about the same as that of a normal nudging term if f, wheref is the Coriolis parameter and is the frequency of the wind oscillation.With 7 Figures     

The effects of orography on precipitation

In this paper, a model simulating the effects of topography and altitude on precipitation is presented. Topography has its maximum effect on precipitation when the angle which the wind makes with the slope direction approaches zero and the inclination of the slope is near 45°. The smaller the angle , the greater the influence of slope on precipitation. When <45°, the larger the inclination, the greater the influence of slope on precipitation and the less the difference in precipitation between the windward and the leeward slopes. When <45°, the reverse holds. But for in the range of 0°–45° and in the range 30°–60°, differences in precipitation on both the windward and leeward slopes are not so well marked and can be neglected in general. In condition of uniform slope inclination, precipitation on the windward slope increases with altitude at first and then decreases after attaining a height (H _m ) of maximum precipitation; alsoH _m is greater, the drier the air mass. When the terrain on the windward side is stepped in shape, it is possible that more than one height of maximum precipitation will occur.     

Equilibrium evaporation beneath a growing convective boundary layer

Expressions for the equilibrium surface Bowen ratio ( _s ) and equilibrium evaporation are derived for a growing convective boundary layer (CBL) in terms of the Bowen ratio at the top of the mixed layer _i and the entrainment parameter A _R . If A_R is put equal to zero, the solution for _s becomes-that previously obtained for the zero entrainment or closed box model. The Priestley-Taylor parameter is also calculated and plotted in terms ofA _R and _i . Realistic combinations of the atmospheric parameters give values of in the range 1.1 to 1.4.     

A generalization of the Kolmogorov-von Kármán relationship and some further implications on the values of the constants

A general relation between the Kolmogorov (₁) and von Kármán (k) constants appropriate to flows in the surface boundary layer is obtained by including stability and divergence dependent terms in the development. The result is used to show that the author's earlier inference of the valuek = 0.36 drawn from the observed value ,k ^4/3=0.141 cannot have been underestimated due to the neglect of stability or divergence effects. It is concluded that if k is to be 0.4, then ₁ must be 0.5.Work performed under the auspices of the U.S. Energy Research and Development Administration.     

The use of σ T as a temperature scale in the atmospheric surface layer

The standard deviation of temperature _T is proposed as a temperature scale and as a velocity scale to describe the behaviour of turbulent flows in the Atmospheric Surface Layer (ASL), instead of _* andu _* of the Monin—Obukhov similarity theory, and ofT _f andU _f used for free convection stability conditions. On the basis of experimental evidence reported in the literature, it is shown that _T T _f andv _* U _f in the free convection region, and _{T *} andv _* U _* in nearneutral and stable conditions. This implies that the proposed scales can be applied for all stabilities. Furthermore, a new length scale is proposed and its relation with Obukhov length is given. Also, a simple semi-empirical expression is presented with which _T andv _* can be evaluated in a rather simple way. Some examples of practical applications are given, e.g., a stability classification for unstable conditions.     

The effect of synoptic-scale advection on the performance of the Priestley-Taylor evaporation formula

Measurements of the appropriate parameters for the calculation of the latent heat flux over a black spruce forest in northern Quebec were carried out in August, 1980. Values of the Priestley-Taylor parameter, , were derived by exploiting the Bowen-ratio-energy-balance (BREB) technique. Derived values of are then related to synoptic-scale warm air advection, derived from surface synoptic charts and tephigrams of the planetary boundary layer. It is found that when warm air advection is present, > 1.26, especially when the surface is wet. When advection enhancement is removed, however, values of approach unity. A new approach to calculating the latent heat flux, when warm air advection is present, is therefore proposed.     

Scavenging Efficiency of ‘Aerosol Carbon’ and Sulfate in Supercooled Clouds at Mt. Sonnblick (3106 m a.s.l., Austria)

Cloud water and interstitial aerosol samples collected at Mt. Sonnblick (SBO) were analyzed for sulfate and aerosol carbon to calculate in-cloud scavenging efficiencies. Scavenging efficiencies for sulfate (_SO) ranged from 0.52 to 0.99 with an average of 0.80. Aerosol carbon was scavenged less efficiently with an average value (_AC) of 0.45 and minimum and maximum values of 0.14 and 0.81, respectively. Both _SO and _AC showed a marked, but slightly different, dependence on the liquid water content (LWC) of the cloud. At low LWC, _SO increased with rising LWC until it reached a relatively constant value of 0.83 above an LWC of 0.3 g/m³. In the case of aerosol carbon, we obtained a more gradual increase of _AC up to an LWC of 0.5 g/m³. At higher LWCs, _{_} remained relatively constant at 0.60. As the differences between _SO and _A varied across the LWC range observed at SBO, we assume that part of the aerosol carbon was incorporated into the cloud droplets independently from sulfate. This hypothesis is supported by size classified aerosol measurements. The differences in the size distributions of sulfate and total carbon point to a partially external mixture. Thus, the different chemical nature and the differences in the size and mixing state of the aerosol particles are the most likely candidates for the differences in the scavenging behavior.     

A Generalized Structure-Activity Relationship for the Decomposition of (Substituted) Alkoxy Radicals

A novel and readily applicable Structure-Activity Relationship (SAR) for predicting the barrier height E_b to decomposition by C-C scission of (substituted) alkoxy radicals is presented. Alkoxy radicals are pivotal intermediates in the atmospheric oxidation of (biogenic) volatile organic compounds, and their fate is therefore of crucial importance to the understanding of atmospheric VOC degradation mechanisms. The SAR is based on available theoretical energy barriers and validated against barriers derived from experimental data. The SAR is expressed solely in terms of the number(s) N_i of alkyl-, hydroxy- and/or oxo-substituents on the - and -carbons of the breaking bond: E_b(kcal/mol) =17.5 – 2.1 × N(alk) – 3.1 ×N(alk) – 8.0 × N_,(OH) – 8.0 × N(O=) – 12 × N(O=). For barriers below 7 kcal/mol, an additional, second-order term accounts for the curvature. The SAR reproduces the available experimental and theoretical data within 0.5 to 1 kcal/mol. The SAR generally allows conclusive predictions as to the fate of alkoxy radicals; several examples concerning oxy radicals from prominent atmospheric VOC are presented. Specific limitations of the SAR are also discussed. Using the predicted barrier height E_b, the high-pressure rate coefficient for alkoxy decomposition k _diss (298 K) can be obtained from k _diss (298 K) = L ×1.8 × 10¹³ exp(–E_b/RT) s^–1, with L the reaction path degeneracy.     

A study of the sensitivity of bare soil evaporation schemes to soil surface wetness,using the coupled soil moisture and surface temperature prediction model,BARESOIL

Summary The performance of evaporation schemes with and approach and their combination within resistance representation of evaporation from bare soil surface is discussed. For this purpose nine schemes, based on different functions of or , on the ratio of the volumetric soil moisture content and its saturated value are used.The quality of the chosen schemes has been evaluated using the results of time integration by the coupled soil moisture and surface temperature prediction model, BARESOIL, using in situ data. A sensitivity analysis was made using two sets of data derived from the volumetric soil moisture content of the top soil layer. One with values below the wilting point (0.17 m³m^–3) and the second with values above 0.20m³m^–3. Data sets were obtained at the experimental site Rimski anevi, Yugoslavia, from the bare surface of a chernozem soil.With 4 Figures     

Evaporation from a blanket bog in a foggy coastal environment

Frequent fog severely restricts evaporation from blanket bogs in Newfoundland because it more than halves the radiant energy input, and it eliminates the vapor pressure deficit, resulting in evaporation at the equilibrium rate (average = 0.99 during fog). During these periods, there is no surface resistance to evaporation because the bog has been wetted by fog drip, and although the latent heat flux dominates over sensible heat (average = 0.8), both are small. In contrast, the surface dries during clear periods, increasing the surface resistance to evaporation so that sensible heat becomes more important ( = 1.05). When the mosses are dry, evaporation is below the equilibrium rate ( = 0.87), although the higher available energy ensures that actual evaporation is higher. During clear periods, daily evaporation averaged 2.5 mm, compared to 1.1 and 0.7 mm for fog and rain, respectively. The suppressed evaporation at this site is important in maintaining appropriate hydrological conditions for blanket bog development.     

Über die mittlere lineare sukzessive Differenz und ihre Anwendung auf die Untersuchung meteorologischer Beobachtungsreihen

Zusammenfassung Eine endliche Reihe (Sequenz) wird als eine der möglichen Permutationen ihrer Glieder aufgefaßt. Es wird gezeigt, daß die Summe der absoluten Differenzen der aufeinanderfolgenden Glieder gleich ist , wo die natürliche Zahlen sind und nur von der Rangordnung der Glieder der Reihe (von der Permutation) abhängen; die _j sind von der Reihenfolge unabhängig und werden durch die Dispersion der Reihenglieder bestimmt. Die _j und die _j werden separat untersucht; der Erwartungswert der erwähnten Differenzsumme wird abgeleitet. Verschiedene bereits bekannte und auch erstmalig hier vorgeschlagene Maßzahlen werden geprüft. An Reihen jährlicher Regenmengen wird die Rolle der _j und der _j und das Verhalten der besprochenen Maßzahlen veranschaulicht.

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Summary A series ofn members can be considered as one of the possible permutations of its members. It is shown that the sum of the linear successive differences is equal to the expression , where the _j are positive integers, dependent only upon the rank-order (the permutation) of the members, while the _j are independent of the order of the succession and are determined by the dispersion of the members of the series. The factors _j and _j are separately investigated; the expected value of the sum of the linear successive differences is established. Various related statistical measures, already in usage and new ones suggested here, are discussed. Series of yearly rainfall amounts are used to show the effects of the _j and _j and to discuss the behaviour of the various measures.

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Résumé Une série, constituée parn valeurs, est regardée comme une des possibles permutations de ces valeurs. L'auteur montre que la somme des différences absolues, qui se présentent entre les valeurs consécutives de la série, est égale à l'expression . Les _j sont des nombres entiers positifs et ne dépendent que de l'ordre des membres de la série, tandis que les _j, indépendants de l'ordre, sont déterminés par la dispersion des membres. Les facteurs _j et _j sont étudiés séparément; l'espérance mathématique de la somme mentionnée est dérivée. Des paramètres statistiques déjà connus ou proposés ici pour la première fois, sont discutés. Le rôle des _j et des _j et le comportement des divers paramètres sont montrés à l'aide de séries de totaux annuels de pluies.

     

Turbulence in a Katabatic Flow

Turbulence measurements performed in a stable boundary layer over the sloping ice surface of the Vatnajökull in Iceland are described. The boundary layer, in which katabatic forces are stronger than the large-scale forces, has a structure that closely resembles that of a stable boundary layer overlying a flat land surface, although there are some important differences. In order to compare the two situations the set-up of the instruments on an ice cap in Iceland was reproduced on a flat grass surface at Cabauw, the Netherlands. Wind speed and temperature gradients were calculated and combined with flux measurements made with a sonic anemometer in order to obtain the local stability functions _m and _h as a function of the local stability parameter z/L. Unlike the situation at Cabauw, where _m was linear as a function of z/L, in the katabatically forced boundary layer, the dependence of _m on stability was found to be non-linear and related to the height of the wind maximum. Thermal stratification and the depth of the stable boundary layer however seem to be rather similar under these two different forcing conditions.Furthermore, measurements on the ice were used to construct the energy balance. These showed good agreement between observed melt and components contributing to the energy balance: net radiation (supplying 55% of the energy), sensible heat flux (30%) and latent heat flux (15%).Local sources and sinks in the turbulent kinetic energy budget are summed and indicate a reasonable balance in near-neutral conditions but not in more stable situations. The standard deviation of the velocity fluctuations _u, _v, and _w, can be scaled satisfactorily with the local friction velocity u_* and the standard deviation of the temperature fluctuation with the local temperature scale _*.     

Gaseous and Particulate Oxidation Products Analysis of a Mixture of α-pinene + β-pinene/O3/Air in the Absence of Light and α-pinene + β-pinene/NOx/Air in the Presence of Natural Sunlight

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/NO_x 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 NO_x 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 NO_x 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.