Henry's law coefficients of formic and acetic acids

The Henry's law constants, K _H, of dilute aqueous formic and acetic acids were determined experimentally as a function of concentration and temperature using a new counterflow packed-column technique. K _H was found to be (8.9±1.3)×10³ and (4.1±0.4)×10³ M atm^-1 at 25°C for HCOOH and CH₃COOH, respectively. The reaction enthalpies, H, were found to be –51±2 kJ mol^-1 and –52±1 kJ mol^-1 for formic and acetic acid, respectively. These are in good agreement with calculated thermochemical values.Whereas the K _H values are in reasonably good agreement with certain other experimentally determined values, K _H (HCOOH) is two to three times higher than calculated thermochemical values while K _H (CH₃COOH) is lower than the two calculated values.The best experimental values appear to be (11±2)×10³ M atm^-1 and (7±3)×10³ M atm^-1 for HCOOH and CH₃COOH, respectively.     

Solubilities of pyruvic acid and the lower (C1-C6) carboxylic acids. Experimental determination of equilibrium vapour pressures above pure aqueous and salt solutions

Henry's law constantsK _H (mol kg^–1 atm^–1) have been determined at 298.15 K for the following organic acids: formic acid (5.53±0.27×10³); acetic acid (5.50±0.29×10³); propionic acid (5.71±0.34×10³);n-butyric acid (4.73±0.18×10³); isobutyric acid (1.13±0.12×10³); isovaleric acid (1.20±0.11×10³) and neovaleric acid (0.353±0.04×10³). They have also been determined fromT=278.15 K toT=308.15 K forn-valeric acid (ln(K _H)=–14.3371+6582.96/T);n-caproic acid (ln(K _H)=–13.9424+6303.73/T) and pyruvic acid (ln(K _H)=–4.41706+5087.92/T). The influence of 9 salts on the solubility of pyruvic acid at 298.15 K has been measured. Pyruvic acid is soluble enough to partition strongly into aqueous atmospheric aerosols. Other acids require around 1 g of liquid water m^–3 (typical of clouds) to partition significantly into the aqueous phase. The degree of partitioning is sensitive to temperature. Considering solubility and dissociation (to formate) alone, the ratio of formic acid to acetic acid in liquid water in the atmosphere (at equilibrium with the gas phase acids) is expected to increase with rising pH, but show little variation with temperature.     

Numerical integration errors in calculated tropospheric photodissociation rate coefficients

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%.     

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.     

High resolution spectral features of a series of aromatic hydrocarbons and BrO: Potential interferences in atmospheric OH-measurements

Naphthalene (C₁₀H₈), several other hydrocarbons, mostly derivates of naphthalene, and bromine oxide (BrO) were analyzed for narrow band (0.01 nm) absorption lines in the wavelength range between 307.7 and 308.3 nm to study their potential impact on OH radical measurements by differential absorption spectroscopy.Only naphthalene showed narrow band absorption lines in this wavelength region. From nine naphthalene lines the differential absorption cross-section was determined.The strongest naphthalene line at 308.002 nm is close to the Q ₁(2) OH line, but about a factor of 200 weaker (=(65.2±15.3)×10^-20 cm²/molec). The corresponding detection limit for naphthalene is about 15 ppt. We re-evaluated some spectra of our OH measurement campaign in July 1987 with respect to naphthalene and obtained an upper limit of 30 ppt for its concentration.BrO was recorded in the larger wavelength interval between 307.7 and 308.7 nm. Structured absorptions were only observed at wavelengths above 308.2 nm and no significant structures were found in the vicinity of the Q ₁(2) and Q ₁(3) OH lines.     

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.     

Free convection scaling over the ocean derived from buoy measurements during gate

The structure of atmospheric turbulence in the surface layer over the open ocean is examined under conditions of local free convection. The raw data consist of profile and fluctuation measurements of wind and temperature as obtained from a meteorological buoy. For near neutral conditions and for waves running approximately along the wind direction, wave-induced wind fluctuations can be described by a simplified linear theory based on Miles (1957). In this case, the spectrum of wind velocity is given as the sum of two parts; for the turbulent part, the parameterization as obtained by Kaimal et al. (1972) applies, while the wave-induced part is parameterized using a simplification of Miles' linear theory. For cases of local free convection, the measurements of the vertical component of the wind velocity are well described by similarity theory; as expected, _w /(-uw)^1/2 is proportional to (- z/L)^1/3. In order to scale the longitudinal wind velocity component, it seems to be reasonable to extend the list of relevant parameters by the height of the mixed layer z _i. We obtain _u /(- uw)^1/2 (z/z _i)^1/3(- z/L)^1/3 with only a poor correlation coefficient of r = 0.6. Overall, the results of local free convection scaling obtained from direct measurements show good agreement with those obtained from profile measurements. A comparison between direct and indirect determination of turbulent fluxes of momentum shows an unexplained difference of about 20%. This discrepancy is mainly due to a gap in the uw-cospectrum at the swell frequency.     

The carbon isotopic ratio of atmospheric carbon dioxide at Tsukuba,Japan

To find out the secular and seasonal trends of the ¹³C value and CO₂ concentration in the surface air and the determination of the ¹³C in the atmospheric CO₂ collected at Tsukuba Science City was carried out during the period from July 1981 to October 1983. The monthly average of the ¹³C value of CO₂ in the surface air collected at 1400 LMT ranged from -7.52 to \s-8.45 with an average of -7.96±0.25 and the CO₂ concentration in the air varied from 334.5 l 1^-1 to 359 l 1^-1 with an average of 347.2±6.3 l 1^-1. The ¹³C value is high in summer and low in winter and is negatively correlated with the CO₂ concentration. In general, the relationship between the ¹³C and the CO₂ concentration is explainable by a simple mixing model of two different constant carbon isotopic species but the relationship does not always follow the model. The correlation between the ¹³C value and the CO₂ concentration is low during the plant growth season and high at other times. The observed negative deviation of the ¹³C value from the simple mixing model in the plant growth season is partly due to the isotopic fractionation process which takes place in the land biota.     

A smog chamber for studies of the reactions of terpenes and alkanes with ozone and OH

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

Kinetics of the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds studied under simulated atmospheric conditions

Rate constants have been measured for the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds by a competitive technique. Mixtures of synthetic air containing a few ppm of nitrous acid, ethylene and the organic substrate were photolysed in a Teflon bag smog chamber. Based on the value k _HO+C2H₄}=8.1×10^-12 cm³ molecule^-1 s^-1 the following rate constants were obtained for the hydroxyl radical reactions at 750 Torr and at 303 K in units of 10^-12 cm³ molecule^-1: CH₃ONO₂, 0.37±0.09; C₂H₅ONO₂, 0.48±0.20; n-C₃H₇ONO₂, 0.70±0.22; C₂H₅OH, 3.6±0.4; CH₃COCH₃, 0.26±0.08; CH₃CO₂ i-C₃H₇, 3.0±0.8; CH₃CO₂ n-C₃H₇, 2.4±0.2. The results are discussed in relation to the available literature data and the implications of the results are considered in terms of the smog reactivity of these molecules.     

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.     

Three-dimensional modeling of synthetic cold fronts interacting with northern Alpine foehn

Summary The effect of the Alpine orography on prototype cold fronts approaching from the west is investigated by three-dimensional numerical model simulations. The numerical experiments cover a range of parameter constellations which govern the prefrontal environment of the front. Especially, the appearance and intensity of prefrontal northern Alpine foehn varies from case to case.The behaviour of a cold front north of the Alps depends much on the prefrontal condition it encounters. It is found that prefrontal foehn can either accelerate or retard the approaching front.An important feature is the pressure depression along the northern Alpine rim that results from the southerly foehn flow. In cases where this depression compensates the eastward directed pressure gradient associated with the largescale flow, the front tends to accelerate and the foehn breaks down as soon as the front passes. In contrast, the foehn prevents the front from a rapid eastward propagation if it is connected with a strong southerly wind component.No-foehn experiments are performed for comparison, where either the mountains are removed, or the static stability is set to neutral. Also shown are effects of different crossfrontal temperature contrasts.List of Symbols c _F propagation speed of a front - x, y horizontal grid spacing (cartesian system) - , horizontal grid spacing (geographic system) - t time step - z vertical grid spacing (cartesian system) - cross-frontal potential temperature difference - _i potential temperature step at an inversion - E turbulent kinetic energy - f Coriolis parameter - FGP frontogenesis parameter (see section 2.2) - g gravity acceleration (g=9.81 m s^–2) - vertical gradient of potential temperature - h terrain elevation (above MSL) - h _i height of an inversion (h _i =1000 m MSL) - H height of model lid (H=9000 m MSL) - K _M exchange coefficient of momentum - K _H exchange coefficient of heat and moisture - longitude - N Brunt-Väisäla-frequency - p pressure - Exner function (=T/) - latitude - q _v specific humidity - R _d gas constant of dry air (R _d =287.06 J kg^–1 K^–1) - density of dry air - t time - T temperature - potential temperature - TFP thermal front parameter (see section 2.2) - u, v, w cartesian wind components - u _g ,v _g geostrophic wind components - horizontal wind vector - x, y, z cartesian coordinates Abbreviations GND (above) ground level - MSL (above) mean sea level - UTC universal time coordinated With 20 Figures     

Carbonyl sulfide emissions from biomass burning in the tropics

Carbonyl sulfide emissions from biomass burning have been studied during field experiments conducted both in an African savanna area (Ivory Coast) and rice fields, central highland pine forest and savanna areas in Viet-Nam. During these experiments CO₂, CO and C₂H₂ or CH₄ have also been also monitored. COS values range from 0.6 ppbv outside the fires to 73 ppbv in the plumes. Significant correlations have been observed between concentrations of COS and CO (R ²=0.92,n=25) and COS and C₂H₂ (R ²=0.79,n=26) indicating a COS production during the smoldering combustion. COS/CO₂ emission factors (COS/CO₂) during field experiments ranged from 1.2 to 61×10^–6 (11.4×10^–6 mean value). COS emission by biomass burning was estimated to be up to 0.05 Tg S/yr in tropics and up to 0.07 Tg S/yr on a global basis, contributing thus about 10% to the global COS flux. Based on the S/C ratio measured in the dry plant biomass and the COS/CO₂ emission factor, COS can account for only about 7% of the sulfur emitted in the atmosphere by biomass burning.     

A review of flux-profile relationships

Flux-profile relationships in the constant flux layer are reviewed. The preferred relationships are found to be those of Dyer and Hicks (1970), namely, _H = _W =(1–16(z/L))^–1/2, _M =(1–16(z/L))^–1/4 for the unstable region, and _H = _W = _M = 1+5(z/L) for the stable region.The carefully determined results of Businger et al. (1971) remain a difficulty which calls for considerable clarification.     

Statistics of Surface-Layer Turbulence Over Terrain with Metre-Scale Heterogeneity

Refuge has patchy vegetation in sandy soil. During midday and at night, the surface sources and sinks for heat and moisture may thus be different. Although the Sevilleta is broad and level, its metre-scale heterogeneity could therefore violate an assumption on which Monin-Obukhov similarity theory (MOST) relies. To test the applicability of MOST in such a setting, we measured the standard deviations of vertical (_w) and longitudinal velocity (_u), temperature (_t), and humidity (_q), the temperature-humidity covariance (¯tq), and the temperature skewness (S_t). Dividing the former five quantities by the appropriate flux scales (u_*, _*, and q_*) yielded the nondimensional statistics _w/u_*, _u/u_*, _t/|t_*|, _q/|q_*|, and ¯tq/t_*q_*. _w/u_*, _t/|t_*|, and S_t have magnitudes and variations with stability similar to those reported in the literature and, thus, seem to obey MOST. Though _u/u_* is often presumed not to obey MOST, our _u/u_* data also agree with MOST scaling arguments. While _q/|q_*| has the same dependence on stability as _t/|t_*|, its magnitude is 28% larger. When we ignore ¯tq/t_*q_* values measured during sunrise and sunset transitions – when MOST is not expected to apply – this statistic has essentially the same magnitude and stability dependence as (_t/t_*)². In a flow that truly obeys MOST, (_t/t_*)², (_q/q_*)², and ¯tq/t_*q_* should all have the same functional form. That (_q/q_*)² differs from the other two suggests that the Sevilleta has an interesting surface not compatible with MOST. The sources of humidity reflect the patchiness while, despite the patchiness, the sources of heat seem uniformly distributed.     

Solubility of HOCl in water and aqueous H2SO4 to stratospheric temperatures

Henry's law constants K_H (mol kg^–1 atm^–1) for the reaction HOCl_(g)=HOCl_(aq) near room temperature, literature data for the associated enthalpy change, and solubilities of HOCl in aqueous H₂SO₄ (46 to 60 wt%) at temperatures relevant to the stratosphere (200 KT230 K) are shown to be thermodynamically consistent. Effective Henry's law constants [H*=mHOCl/pHOCl, in mol kg^–1 atm^–1] of HOCl in aqueous H₂SO₄ are given by: ln(H*)=6.4946–mH₂SO₄(–0.04107+54.56/T)–5862 (1/T_o–1/T) where T(K) is temperature and T_o=298.15K. The activity coefficient of HOCl in aqueous H₂SO₄ has a simple Setchenow-type dependence upon H₂SO₄ molality.     

A laboratory study of the mechanism of the oxygen airglow

Further laboratory studies of emission by O(¹ S) and by O₂ A ³ _u ⁺ ,A³ _u andc ¹ _u ^– in the oxygen afterglow lead to the conclusion that Barth's mechanism for the excitation of the auroral green line O ₂ ^* +O(³P=O₂+O(¹S)–(1) is correct and that levelsv=6 and 7 of O₂ A ³ _u ⁺ are Barth precursors. The value ofk ₁=7×10^–11 cm³ s^–1 deduced for these levels is shown to be in fair agreement with atmospheric measurements.     

Variations in atmospheric CO2 at the Meteorological Research Institute, Tsukuba, Japan

Since April 1986, measurements of the CO₂ concentration in the surface air have been conducted at the Meteorological Research Institure (MRI, 36°04 N, 140°07 E, 25 m above sea level) in Tsukuba, located 50 km northeast of Tokyo, Japan. The CO₂ data measured over times between 11:00 Japan Standard Time (JST) and 16:00 JST (C _N ) were considered to be representative of the air (within a few ppmv) in the planetary boundary layer. To evaluate the representative CO₂ level on a spatial scale larger than that of the C _N record, the CO₂ data with hour-to-hour variation less than 1 ppmv were selected (C _P ). Comparison of these data with those of Ryori (39°02 N, 141°50 E), a continental station operated by the Japan Meteorological Agency, indicates that the C _P record provides a representative CO₂ level in the air on spatial scales of at least a few hundred kilometers.The C _N record allows an investigation of the internanual changes in photosynthesis/respiration against changes in climatological parameters. Within a small temperature anomaly (ca.±1 °C) respiration is sensitive to the temperature change, while photosynthesis is less sensitive. When the temperature anomaly is large, however, photosynthesis and respiration tend to be competitive.     

Microwave vegetation optical depth and inverse modelling of soil emissivity using Nimbus/SMMR satellite observations

Summary A radiative transfer model has been used to determine the large scale effective 6.6 GHz and 37 GHz optical depths of the vegetation cover. Knowledge of the vegetation optical depth is important for satellite-based large scale soil moisture monitoring using microwave radiometry. The study is based on actual observed large scale surface soil moisture data and observed dual polarization 6.6 and 37 GHz Nimbus/SMMR brightness temperatures over a 3-year period. The derived optical depths have been compared with microwave polarization differences and polarization ratios in both frequencies and with Normalized Difference Vegetation Index (NDVI) values from NOAA/AVHRR. A synergistic approach to derive surface soil emissivity from satellite observed brightness temperatures by inverse modelling is described. This approach improves the relationship between satellite derived surface emissivity and large scale top soil moisture fromR ²=0.45 (no correction for vegetation) toR ²=0.72 (after correction for vegetation). This study also confirms the relationship between the microwave-based MPDI and NDVI earlier described and explained in the literature.List of Symbols f frequency [Hz] - f _i(p) fractional absorption at polarizationp - h surface roughness - h h cos² - H horizontal polarization - n _i complex index of refraction - p polarization (H orV) - R _s microwave surface reflectivity - T _B(p) brightness temperature at polarizationp - T ^* normalized brightness temperature - T polarization difference (T _v-T _H) - T _s temperature of soil surface - T _c temperature of canopy - T _max daily maximum air temperature - T _min daily minimum air temperature - V vertical polarization - soil moisture distribution factor; also used for the constant to partition the influence of bound and free water components to the dielectric constant of the mixture - empirical complex constant related to soil texture - microwave transmissivity of vegetation (=e ^–) - ^* effective transmissivity of vegetation (assuming =0) - microwave emissivity - _s emissivity of smooth soil surface - _rs emissivity of rough soil surface - _vs emissivity of vegetated surface - soil moisture content (% vol.) - K dielectric constant [F·m^–1] - K _fw dielectric constant of free water [F·m^–1] - K _ss dielectric constant of soil solids [F·m^–1] - K _m dielectric constant of mixture [F·m^–1] - K _o permittivity of free space [8.854·10^–12 F·m^–1] - high frequency limit ofK _wf [F·m^–1] - wavelength [m] - incidence angle [degrees from nadir] - polarization ratio (T _H/T _V) - b soil bulk density [gr·cm^–3] - s soil particle density [gr·cm^–3] - R surface reflectivity in red portion of spectrum - NIR surface reflectivity in near infrared portion of spectrum - _eff effective conductivity of soil extract [mS·cm^–1] - vegetation optical depth - _6.6 vegetation optical depth at 6.6 GHz - ₃₇ vegetation optical depth at 37 GHz - ^* effective vegetation optical depth (assuming =0) - single scattering albedo of vegetation With 12 Figures     

Effect of finite sampling on atmospheric spectra

The effect of a finite averaging time on variances is well known, but its effect on power spectra is less clearly understood. We present numerical solutions for the spectral distortion arising from sampling over a finite time interval T and show that the commonly used filter function (1 – sinc²f T), valid for variances, is a reasonable approximation for power spectra only when T 10 _m , where f is the cyclic frequency, and _m is the dominant time scale of the process. Our results exhibit an increasingly steeper low-frequency roll-off as T decreases relative to _m , indicating that the measured spectrum is subject to a greater suppression of the lower frequencies (f > 1/T) than predicted by (1 – sinc²f T). This suppression is, in a sense, compensated by an overestimation of spectral estimates in the frequency range f 1/T.