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.     

The behaviour of a mixed-layer model of the convective boundary layer coupled to a big leaf model of surface energy partitioning

Daily mean values of the Priestley-Taylor coefficient, ¯, are derived from a simple model of the daily growth of a convective boundary layer. For a particular control set of driving environmental variables, ¯ is related to the prescribed bulk surface resistance, r_S by 1/¯ = 1/₀ + mr_S for parameters ₀ and m. The dependence of the parameters ₀ and m on weather is explored and a potential use of this linear relation to provide information about regional values of r_S is indicated.     

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 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.     

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.     

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     

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.     

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.

---

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.

---

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.

     

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.     

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.     

A SIMPLE FORMULA FOR ATTENUATION OF EDDY FLUXES MEASURED WITH FIRST-ORDER-RESPONSE SCALAR SENSORS

A simple formula, (1 + (2fmc))-1,is proposed to estimate the attenuation of a scalar flux measurement made by eddy-correlation using a fast-response anemometer and a linear, first-order-response scalar sensor with a characteristic time constant c.In this formula, =7/8 for neutral and unstable stratification within the surface-flux layer and =1 both within the convective boundary layer (CBL) and for stable stratification in the surface layer.fm is the frequency of the peak of the logarithmic cospectrum and can be estimated from fm = nm /z, where z is the measurement height and is thewind speed at that height. The dimensionless frequency at the cospectral maximum nm is estimated here from observations of its behavioras a function of atmospheric stability, z/L within the surface layeror z/zi within the CBL, where L is the Obukhov stability length and zi is the depth of the CBL. The predicted dependence of flux attenuation on measurement height is discussed.     

Transport-Dissipation Analytical Solutions to the E-∈Turbulence Model and their Role in Predictions of the Neutral ABL

E- turbulence model predictions of the neutralatmospheric boundary layer (NABL) are reinvestigated to determine thecause for turbulence overpredictions found in previous applications. Analytical solutions to the coupled E and equations for the case of steady balance between transport and dissipation terms, the dominant balance just below the NABL top, are derived. It is found that analytical turbulence profiles laminarizeat a finite height only for values of closure parameter ratio c ₂ /_e equal toor slightly greater than one, with laminarization as z for greater . The point = 2 is additionally foundthat where analytical turbulent length scale (l) profilesmade a transition from ones ofdecreasing ( < 2) to increasing ( > 2)values with height. Numerically predicted profiles near the NABL topare consistent with analytical findings. The height-increasingvalues of l predicted throughout the NABL with standard values ofclosure parameters thus appear a consequence of 2.5(> 2), implied by these values (c ₂ = 1.92, _{= 1.3}, _{e = 1}). Comparison of numericalpredictions with DNS data shows that turbulence overpredictions obtained with standard-valued parameters are rectifiedby resetting and _e to 1.1 and 1.6, respectively, giving, with c ₂ = 1.92, 1.3, and laminarization of the NABL's cappingtransport-dissipation region at a finite height.     

Reactions of alkoxy radicals under atmospheric conditions: The relative importance of decomposition versus reaction with O2

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)=(H_{decomposition}–H_{O 2 reaction}), between these two reactions pathways. For (H)[22–0.5(H_{O 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(H_{O 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.     

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     

Calculation of sensible and latent heat fluxes,and surface resistance from profile data

A set of semi-continuous measurements of temperature, wind and moisture gradients as well as of net radiation and ground heat flux covering a period of about one and a half years has been analysed to give a corresponding set of complete surface energy balance data on an hourly basis. An analysis of the evaporation data so obtained is given.It is shown that surface resistance r _S exhibits a diurnal trend: values are smallest (ca. 150 s m^-1) a few hours before noon and increase to as much as 800 s m^-1 towards dusk. The minimum values tend to be higher during dry periods when the soil moisture is low. There is also some indication that r _S decreases rapidly soon after rainfall.An exponential relation is found between the fraction of available energy used as evaporative flux, , and r _S for values of r _I/r_S <0.70, where r _I is the climatological resistance. On the other hand, the ratio of r _I to r _S is linearly correlated with , implying that an equilibrium state is established between the grass surface and the atmosphere, at least from mid-morning to mid-afternoon when the leaves are dry. Near-noon values calculated by Stewart and Thom for Thetford Forest also follow a linear trend.The above two regression results (In (r _S) versus r _I/r_S versus ) are combined to obtain an empirical relation of the form r _I=m exp (a-b) which is used to estimate evaporative flux. The estimates are found to be within 20% of calculated values.Guest Scientist from Department of Physics, University of Cape Coast, Cape Coast, Ghana.     

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.     

Diurnal variation of horizontal wind direction fluctuations in complex terrain at Geysers,Cal.

Horizontal diffusion in the surface layer is dependent on the standard deviation of wind direction fluctuations . Diurnal variation of this parameter in complex terrain was studied for the July 1979 Geysers, Cal., experiment using data from a network of 11 short meteorological towers in the 25 km² Anderson Creek watershed Valley side slopes are roughly 20 ° and maximum terrain difference is about 1 km.Values of for wind directions sampled for one hour at a height of 10 m are about 35 ° during the daytime. They slowly decrease to about 20 ° by 8 to 10 p.m. as stability increases but wind speeds are still relatively high. After 10 p.m. the drainage flow sets in at most stations, with speeds of 1 to 2 m s^-1, and average increases to about 30° during the period 11 p.m. to 6 a.m. In general, highest values of at night are associated with lowest values of wind speed and greatest static stability. This enhancement of by the terrain suggests that horizontal diffusion at night always conforms to that expected during nearly neutral stabilities. That is, Pasquill class D diffusion applies to the horizontal component all night in complex terrain.     

On the representation of frequency spectra in meteorology

The common representation of frequency spectra in meteorology and climatology is discussed. It is pointed out that this representation is misleading since spectral peaks and spectral gaps are obtained even when the spectrum density is monotonously decreasing in the whole frequency range. A plea is made for using the spectrum distribution function, F() which gives an unambiguous picture of the distribution of variance with frequency.     

Northern hemisphere atmospheric response to changes of atlantic ocean SST on decadal time scales: a GCM experiment

Analyses indicate that the Atlantic Ocean seasurface temperature (SST) was considerably colder at the beginning than in the middle of the century. In parallel, a systematic change in the North Atlantic sea-level pressure (SLP) pattern was observed. To find out whether the SST and SLP changes analyzed are consistent, which would indicate that the SST change was real and not an instrumental artifact, a response experiment with a low-resolution (T21) atmospheric GCM was performed. Two perpetual January simulations were conducted, which differ solely in the Atlantic Ocean (40° S-60° N) SST: the cold simulation utilizes the SSTs for the period 1904–1913; the warm simulation uses the SSTs for the period 1951–1960. Also, a control run with the model's standard SST somewhat between the cold and warm SST was made. For the response analysis, a rigorous statistical approach was taken. First, the null hypothesis of identical horizontal distributions was subjected to a multivariate significance test. Second, the level of recurrence was estimated. The multivariate statistical approaches are based on hierarchies of test models. We examined three different hierarchies: a scale-dependent hierarchy based on spherical harmonics (S), and two physically motivated ones, one based on the barotropic normal modes of the mean 300 hPa flow (B) and one based on the eigenmodes of the advection diffusion operator at 1000 hPa (A). The intercomparison of the cold and warm experiments indicates a signal in the geostrophic stream function that in the S-hierarchy is significantly nonzero and highly recurrent. In the A-hierarchy, the low level temperature field is identified as being significantly and recurrently affected by the altered SST distribution. The SLP signal is reasonably similar to the SLP change observed. Unexpectedly, the upper level stream-function signal does not appear to be significantly nonzero in the B-hierarchy. If, however, the pairs of experiments warm versus control and cold versus control are examined in the B-hierarchy, a highly significant and recurrent signal emerges. We conclude that the cold versus warm response is not a small disturbance that would allow the signal to be described by eigenmodes of the linear system. An analysis of the three-dimensional structure of the signal leads to the hypothesis that two different mechanisms are acting to modify the model's mean state. At low levels, local heating and advection are dominant, but at upper levels the extratropical signal is a remote responce to modifications of the tropical convection.This paper was presented at the International Conference on Modelling of Global Climate Change and Variability, held in Hamburg 11–15 September 1989 under the auspices of the Meteorological Institute of the University of Hamburg and the Max Planck Institute for Meteorology. Guest Editor for these papers is Dr. L. Dilmenil.AWI Publication no. 254     

On the inner-layer scale height of boundary-layer flow over low hills

Jackson and Hunt's (1975) equation for the depth of the inner layer of flows over low hills does not depend on any closure assumption as contrarily supposed in literature. This equation contains a constant which can arbitrarily be specified. It is suggested that this inner-layer constant should be determined from experimental data. A preliminary check with some data from the Askervein experiment suggests that Jackson and Hunt's equation fits these data almost as well as Jensen's equation provided that fitted inner-layer constants are used.