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.     

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.     

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.     

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 Influence of O3, Relative Humidity, NO and NO2 on the Oxidation of α-Pinene and Δ3-Carene

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.     

Monoterpene concentrations in and above a forest of scots pine

Diurnal and vertical ambient air measurements of the monoterpenes have been made in and above a Scots pine (Pinus sylvestris) forest of central Sweden, within the boreal northern coniferous biome. Sampling was done with Tenax TA, and analysis by GC and ion trap detection. Daytime mixing ratios were on the order of tenths of a ppbv from the forest floor to the top of the forest, and a factor of 2 or 3 lower above the forest. Mixing ratios at night were at the ppbv level, highest near the forest floor and the crown, and decreased with height above the forest. The highest total concentration observed was 8 ppbv inside the forest at 3 am (GMT). The average terpene composition was 3-carene 32%, -pinene 29%, limonene 18%, -pinene 10%, -phellandrene 7%, camphene 5%, and sabinene at less than 2%. The 3-carene/-pinene ratio varied with wind direction and speed, relative humidity, and wet/dry vegetation, but not with ozone or NO₂ concentration, solar radiation, or temperature. Variations in the observed terpene composition at the sampling site are mainly caused by the influence of other vegetation in the vicinity of the site. It would seem that wet Scots pine emits more 3-carene relative to -pinene than does dry pine.     

Nitrate in the atmospheric boundary layer of the tropical South Pacific: Implications regarding sources and transport

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.     

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     

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     

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     

Formation of Organic Aerosols from the Oxidation of Biogenic Hydrocarbons

Measurements of aerosol formation during thephotooxidation of -pinene, -pinene,d-3-carene, d-limonene, ocimene, linalool, terpinene-4-ol, andtrans-caryophyllene were conducted in anoutdoor smog chamber. Daylight experiments in thepresence of and dark experiments withelevated ozone concentrations were performed. Theevolution of the aerosol was simulated by theapplication of a gas/particle absorption model inconnection with a chemical reaction mechanism. Thefractional aerosol yield is shown to be a function ofthe organic aerosol mass concentration andtemperature. Ozone and, for selected hydrocarbons, theNO₃ reaction of the compounds were found torepresent efficient routes to the formation ofcondensable products. For initial hydrocarbon mixingratios of about 100 ppb, the fractional aerosol yieldsfrom daylight runs have been estimated to be 5%for open-chain hydrocarbons, such as ocimene andlinalool, 5–25% for monounsaturated cyclicmonoterpenes, such as -pinene, d-3-carene, orterpinene-4-ol, and 40% for a cyclic monoterpenewith two double bonds like d-limonene. For the onlysesquiterpene investigated, trans-caryophyllene, afractional aerosol yield of close to 100% wasobserved. The majority of the compounds studied showedan even higher aerosol yield during dark experimentsin the presence of ozone.     

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.     

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.     

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.     

Ly(α) absorption cross-section of H2O and O2

The absorption cross-sections of water vapor and oxygen were measured, using a low-pressure radio frequency discharge through traces of hydrogen in argon as a light source for Ly() radiation. The cross-sections are H₂O = 1.59 × 10^–17 cm² and O₂ = 1.13 × 10^–20 + 1.72 × 10^–23 for water and oxygen, respectively, where P is the oxygen pressure in units of Torr. Ly() lamps, such as used for this work, are important light sources for photochemical laboratory work and find applications for trace-gas detection in the atmosphere. For the latter application, accurate cross-sections of water vapor and oxygen are needed.     

Emissions of Volatile Organic Compounds from Sunflower and Beech: Dependence on Temperature and Light Intensity

Emissions of volatile organic compounds (VOCs) from sunflower (Helianthus annuus L. cv. giganteus) were measured in a continuously stirred tank reactor. The compounds predominantly emitted from sunflower were: isoprene, the monoterpenes -pinene, -pinene, sabinene, 3-carene and limonene, an oxygenated terpene, not positively identified so far and the sesquiterpene -caryophyllene. Emission rates ranged from 0.8 x 10^–16 to 4.3 x 10 ^–15 mol cm^–2 s^–1 at a temperature of 25°C and at a light intensity of 820 µEm^–2 s^–1. A dependence of the emission rates on temperature as well as on light intensity was observed. The emission rates of -pinene, sabinene and thujene from beech (Fagus sylvatica L.) were also affected by temperature as well as by light intensity. Our results suggest that an emission algorithm for all compounds emitted from sunflower and beech has to consider temperature and light intensity simultaneously. The observations strongly indicate that the emissions of VOCs from sunflower and beech are in part closely coupled to the rate of biosynthesis and in part originate from diffusion out of pools. The emission rates can be described by an algorithm that combines the model given by Tingey and coworkers with the algorithm given by Guenther and coworkers after slight modification.     

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.     

Application of the Priestley-Taylor evaporation model to assess the influence of soil moisture on the evaporation from a large weighing lysimeter and class a pan

The influence of soil moisture on evaporation from a 6-m grass-covered lysimeter and from Class A pans was assessed for one summer using the -parameter of the Priestley-Taylor evaporation model appropriate for the individual surfaces computed on a daily basis. Net radiation over the pan was estimated from above-grass measurements using a correlation established between the two, using measurements made in the previous two summers. Changes in heat storage of the water were considered in the derivation of for the pan. A unique relationship for the particular conditions of the site was determined between the for the lysimeter and soil moisture, approaching 1.29 at soil moisture near field capacity, but decreasing to as low as 0.5 for dry soil. The corresponding relationship for the pan showed more scatter, but this was improved by using 5-day running means of evaporation and stratifying the data in terms of wind speed to yield a family of curves. Values for at wet soil conditions varied from 1.07 for 100 km day^–1 wind run to 1.17 for 250 km day^–1 wind run. For each curve, values of increased by about 20%; as the soil dried. The relationships may be used to reduce observed Class A pan evaporation to equivalent values for wet-soil conditions and to estimate near-surface soil moisture and actual evapotranspiration for this particular site. Extension of the technique to other areas requires derivation of similar relationships appropriate for those other locations     

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.     

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.