Comparison of flux measurements with open- and closed-path gas analyzers above an agricultural field and a forest floor

Comparison was made of the flux measurements of a closed-path CO₂/H₂O analyzer and an open-path H₂O analyzer above a clover field and the forest floor of a Douglas-fir stand. The attenuation of the gas concentration fluctuations caused by the sampling tube of the closed-path analyzer resulted in underestimation of the H20 flux above both surfaces. The degree of underestimation above the clover field depended on wind speed, but was smaller than that calculated from the transfer function for laminar flow in a circular tube and the scalar cospectrum in the neutral and unstable surface layer. Above the forest floor CO₂ fluctuations led those of H₂O by 0.7s. The implications of this are discussed regarding the determination of the time delay caused by the sampling tube of the closedpath analyzer. The day-time CO₂ efflux from the forest floor, averaged over three days, was 0.043 mg/(m²s).     

The Henry's Law Constants of the Haloacetic Acids

Henry's law constants K_H (mol kg^-1 atm^-1) have been measured between 278.15 K and 308.15 K for the following organic acids: CH₂FCOOH (ln(K_H[298.15 K]) = 11.3 ± 0.2), CH₂ClCOOH (11.59 ± 0.14), CH₂BrCOOH (11.94 ± 0.21), CHF₂COOH (10.32 ± 0.10), CHCl₂COOH (11.69 ± 0.11), CHBr₂COOH (12.33 ± 0.29), CBr₃COOH (12.61 ± 0.21), and CClF₂COOH (10.11 ± 0.12). The variation of K_H with temperature was determined for all acids except CH₂FCOOH and CBr₃COOH, with _r H° for the dissolution reaction ranging from –85.2 ± 2.6 to –57.1 ± 2.5 kJ mol^-1, meaning that their solubility is generally more sensitive to temperature than is the case for the simple carboxylic acids. The Henry's law constants show consistent trends with halogen substitution and, together with their high solubility compared to the parent (acetic) acid (ln(K_H[298.15 K]) = 8.61), present a severe test of current predictive models based upon molecular structure. The solubility of haloacetic acids and strong dissociation at normal pH mean that they will partition almost entirely into cloud and fog in the atmosphere (0.05–1.0 g H₂O m^-3), but can reside in both phases for the liquid water contents typical of aerosols (10^-5-10^-4 g H₂O m^-3).     

Influences on surface energy fluxes in simulated present and doubled CO2 climates

The surface energy fluxes simulated by the CSIRO9 Mark 1 GCM for present and doubled CO₂ conditions are analyzed. On the global scale the climatological flux fields are similar to those from four GCMs studied previously. A diagnostic calculation is used to provide estimates of the radiative forcing by the GCM atmosphere. For 1 × CO₂, in the global and annual mean, cloud produces a net cooling at the surface of 31 W m^–2. The clear-sky longwave surface greenhouse effect is 311 W m^–2, while the corresponding shortwave term is –79 W m^–2. As for the other GCM results, the CSIRO9 CO₂ surface warming (global mean 4.8°C) is closely related to the increased downward longwave radiation (LW ). Global mean net cloud forcing changes little. The contrast in warming between land and ocean, largely due to the increase in evaporative cooling (E) over ocean, is highlighted. In order to further the understanding of influences on the fluxes, simple physically based linear models are developed using multiple regression. Applied to both 1 × CO₂ and CO₂ December–February mean tropical fields from CSIRO9, the linear models quite accurately (3–5 W m^–2 for 1 × CO₂ and 2–3 W m^–2 for CO₂) relate LW and net shortwave radiation to temperature, surface albedo, the water vapor column, and cloud. The linear models provide alternative estimates of radiative forcing terms to those from the diagnostic calculation. Tropical mean cloud forcings are compared. Over land, E is well correlated with soil moisture, and sensible heat with air-surface temperature difference. However an attempt to relate the spatial variation of LWt within the tropics to that of the nonflux fields had little success. Regional changes in surface temperature are not linearly related to, for instance, changes in cloud or soil moisture.     

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.     

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.     

Determination of heterogeneous reaction probability using deposition profile measurement in an annular reactor: Application to the N2O5/H2O reaction

A method for the estimation of the reaction probability of the heterogeneous N₂O₅+H₂O 2HNO₃ reaction using the deposition profile in a laminar flow tube, in which the walls are coated with the condensed aqueous phase of interest, is presented. The production of gas phase nitric acid on the surface followed by its absorption complicates the deposition profiles and hence the calculation of the reaction probability. An estimation of the branching ratio for this process enables a more appropriate calculation to be carried out. Reaction probabilities of N₂O₅ on substances including some normally constituting atmospheric aerosols, NaCl, NH₄HSO₄, as well as Na₂CO₃ are estimated and found to depend on relative humidity and characteristics of the coating used. These fell within the range (0.04–2.0)×10^–2.     

A global model of changing N2O emissions from natural and perturbed soils

A high resolution global model of the terrestrial biosphere is developed to estimate changes in nitrous oxide (N₂O) emissions from 1860–1990. The model is driven by four anthropogenic perturbations, including land use change and nitrogen inputs from fertilizer, livestock manure, and atmospheric deposition of fossil fuel NO _x . Global soil nitrogen mineralization, volatilization, and leaching fluxes are estimated by the model and converted to N₂O emissions based on broad assumptions about their associated N₂O yields. From 1860–1990, global N₂O emissions associated with soil nitrogen mineralization are estimated to have decreased slightly from 5.9 to 5.7 Tg N/yr, due mainly to land clearing, while N₂O emissions associated with volatilization and leaching of excess mineral nitrogen are estimated to have increased sharply from 0.45 to 3.3 Tg N/yr, due to all four anthropogenic perturbations. Taking into account the impact of each perturbation on soil nitrogen mineralization and on volatilization and leaching of excess mineral nitrogen, global 1990 N₂O emissions of 1.4, 0.7, 0.4 and 0.08 Tg N/yr are attributed to fertilizer, livestock manure, land clearing and atmospheric deposition of fossil fuel NO _x , respectively. Consideration of both the short and long-term fates of fertilizer nitrogen indicates that the N₂O/fertilizer-N yield may be 2% or more.C. NBM Definitions AET _mon (cm H₂O) = monthly actual evapotranspiration - AET _ann (cm H₂O) = annual actual evapotranspiration - age _h (years) = stand age of herbaceous biomass - age _w (years) = stand age of woody biomass - atmblc (gC/m²/month) = net flux of CO₂ from grid - biotoc (gC/g biomass) = 0.50 = convert g biomass to g C - beff _h = 0.8 = fraction of cleared herbaceous litter that is burned - beff _w = 0.4 = fraction of cleared woody litter that is burned - bfmin = 0.5 = fraction of burned N litter that is mineralized or converted to reactive gases which rapidly redeposit. Remainder assumed pyrodenitrified to N₂. + N₂O - bprob = probability that burned litter will be burned - burn _h (gC/m²/month) = herbaceous litter burned after land clearing - burn _w (gC/m²/month) = woody litter burned after land clearing - cbiomsh (gC/m²) = C herbaceous biomass pool - cbiomsw (gC/m²) = C woody biomass pool - clear (gC/m²/month) = woody litter C removed by land clearing - clearn (gN/m²/month) = woody litter N removed by land clearing - cldh (month^–1) = herbaceous litter decomposition coefficient - cldw (month^–1) = woody litter decomposition coefficient - clittrh (gC/m²) = C herbaceous litter pool - clittrw (gC/m²) = C woody litter pool - clph (month^–1) = herbaceous litter production coefficient - clpw (month^–1) = woody litter production coefficient - cnrath (gC/gN) = C/N ratio in herbaceous phytomass - cnrats (gC/gN) = C/N ratio in soil organic matter - cnratt (gC/gN) = average C/N ratio in total phytomass - cnratw (gC/gN) = C/N ratio in woody phytomass - crod (month^–1) = forest clearing coefficient - csocd (month^–1) = actual soil organic matter decompostion coefficient - decmult decomposition coefficient multiplier; natural =1.0; agricultural =1.0 (1.2 in sensitivity test) - fertmin (gN/m²/month) = inorganic fertilizer input - fleach fraction of excess inorganic N that is leached - fligh (g Lignin/ g C) = lignin fraction of herbaceous litter C - fligw (g Lignin/ g C) = 0.3 = lignin fraction of woody litter C - fln2o = .01–.02 = fraction of leached N emitted as N₂O - fnav = 0.95 = fraction of mineral N available to plants - fosdep (gN/m²/month) = wet and dry atmospheric deposition of fossil fuel NO _x - fresph = 0.5 = fraction of herbaceous litter decomposition that goes to CO₂ respiration - fresps = 0.51 + .068 ^* sand = fraction of soil organic matter decomposition that goes to CO₂ respiration - frespw = 0.3 ^* (^* see comments in Section 2.3 under decomposition) = fraction of woody litter decomposition that goes to CO₂ respiration - fsoil = ratio of NPP measured on given FAO soil type to NPF_miami - fstruct = 0.15 + 0.018 ^* ligton = fraction of herbaceous litter going to structural/woody pool - fvn2o = .05–.10 = fraction of excess volatilized mineral N emitted as N₂O - fvol = .02 = fraction of gross mineralization flux and excess mineral N volatilized - fyield ratio of total agricultural NPP in a given country in 1980 to total NPP_miami of all displaced natural grids in that country - gimmob _h (gN/m²/month) = gross immobilization of inorganic N into microbial biomass due to decomposition of herbaceous litter - gimmob _s (gN/m²/month) = gross immobilization of inorganic N into microbial biomass due to decomposition of soil organic matter - gimmob _w (gN/m²/month) = gross immobilization of inorganic N into microbial biomass due to decomposition of woody litter - graze (gC/m²/month) = C herbaceous biomass grazed by livestock - grazen (gN/m²/month) = N herbaceous biomass grazed by livestock - growth _h (gC/m²/month) = herbaceous litter incorporated into microbial biomass - growth _w (gC/m²/month) = woody litter incorporated into microbial biomass - gromin _h (gN/m²/month) = gross N mineralization due to decomposition and burning of herbaceous litter - gromin _s (gN/m²/month) = gross N mineralization due to decomposition of soil organic matter - gromin _w (gN/m²/month) = gross N mineralization due to decomposition and burning of woody litter - herb herbaceous fraction by weight of total biomass - leach (gN/m²/month) = leaching (& volatilization) losses of excess inorganic N - ligton (g lignin-C/gN) = lignin/N ratio in fresh herbaceous litter - LP _h (gC/m²/month)= C herbaceous litter production - LP (gC/m²/month) = C woody litter production - LPN _h (gN/m²/month) = N herbaceous litter production - LPN _W (gN/m²/month) = N woody litter production - manco2 (gC/m²/month) = grazed C respired by livestock - manlit (gC/m²/month) = C manure input (feces + urine) - n2oint (gN/m²/month) = intercept of N₂O flux vs gromin regression - n2oleach (gN/m²/month) = N₂O flux associated with leaching and volatilization of excess inorganic N - n2onat (gN/m²/month) = natural N₂O flux from soils - n2oslope slope of N₂O flux vs gromin regression - nbiomsh (gN/m²) = N herbaceous biomass pool - nbiomsw (gN/m²) = N woody biomass pool - nfix (gN/m²/month) = N₂ fixation + natural atmospheric deposition - nlittrh (gN/m²) = N herbaceous litter pool - nlittrw (gN/m²) = N woody litter pool - nmanlit (gN/m²/month) = organic N manure input (feces) - nmanmin (gN/m²/month) = inorganic N manure input (urine) - nmin (gN/m²) = inorganic N pool - NPP _acth (gC/m²/month)= actual herbaceous net primary productivity - NPP _actw (gC/m²/month) = actual woody net primary productivity - nvol (gN/m²/month) = volatilization losses from inorganic N pool - plntnav (gN/m²/month)= mineral N available to plants - plntup _h (gN/m²/month) = inorganic N incorporated into herbaceous biomass - plntup _w (gN/m²/month) = inorganic N incorporated into woody biomass - precip _ann (mm) = mean annual precipitation - precip _mon (mm) = mean monthly precipitation - pyroden _h (gN/m²/month) = burned herbaceous litter N that is pyrodenitrified to N₂ - pyroden _w (gN/m²/month) = burned woody litter N that is pyrodenitrified to N₂ - recyc fraction of N that is retranslocated before senescence - resp _h (gC/m²/month) = herbaceous litter CO₂ respiration - resp _s (gC/m²/month) = soil organic carbon CO₂ respiration - resp _w (gC/m²/month) = woody litter CO₂ respiration - sand sand fraction of soil - satrat ratio of maximum NPP to N-limited NPP - soiloc (gC/m²) = soil organic C pool - soilon (gN/m²) = soil organic N pool - temp _ann (°C) = mean annual temperature - temp _mon (°C) = mean monthly temperature Now at the NOAA Aeronomy Laboratory, Boulder, Colorado.     

Carbon dioxide,water vapor and sensible heat exchanges of a grain sorghum canopy

With the aid of eddy correlation instrumentation, the components of the energy budget and CO₂ flux were measured over grain sorghum grown at Mead, Nebraska. Diurnal patterns of sensible heat, latent heat, CO₂ and momentum flux are examined for typical days. On a mostly clear day when the crop leaf area index was 3.7, net radiation reached a mid-day peak of 560 W m^-2, while sensible and latent heat fluxes peaked at 50 and 460 W m^-2, respectively. The peak CO₂ flux occurring just prior to solar noon was 1.5 mg m^-2(ground area) s^-1. CO₂ flux (respiration from plants, soil and roots) in the early evening was about -0.28 mg m^-2 (ground area) s^-1.A relationship between CO₂ flux and photosynthetically active radiation (PAR) was developed. Except during the late stage of growth (growth stage 8.5, toward the initiation of senescence), the crop showed no evidence of saturation up to PAR 1800 Ei m^-2s^-1. The light compensation point was found to be about 211 Ei m^-2s^-1. Examination of CO₂ flux-PAR relationships for selected days through the season indicated an aging effect in terms of a decrease in photosynthetic activity of the sorghum canopy. Measurements made on two consecutive days demonstrate the effects of weather conditions on CO₂ flux and carbon-water flux ratio (a measure of water use efficiency of the crop). The occurrence of regional sensible heat advection with concommitant high vapor pressure deficit and air temperature-limited CO₂ exchange reduced the carbon-water flux ratio.Published as Paper No. 7717, Journal Series, Nebraska Agricultural Research Division. The work was conducted under Regional Research Project 11-33 and Nebraska Agricultural Research Division Project 27-003.Formerly Post Doctoral Research Associate (now at the University of Connecticut Department of Renewable Natural Resources Storrs CT)     

Eddy correlation measurements of CO2, latent heat,and sensible heat fluxes over a crop surface

Eddy correlation equipment was used to measure mass and energy fluxes over a soybean crop. A rapid response CO₂ sensor, a drag anemometer, a Lyman-alpha hygrometer and a fine wire thermocouple were used to sense the fluctuating quantities.Diurnal fluxes of sensible heat, latent heat and CO₂ were calculated from these data. Energy budget closure was obtained by summing the sensible and latent heat fluxes determined by eddy correlation which balanced the sum of net radiation and soil heat flux. Peak daytime CO₂ fluxes were near 1.0 mg m^–2 (ground area) s^–1.The eddy correlation technique was also employed in this study to measure nocturnal CO₂ fluxes caused by respiration from plants, soil, and roots. These CO₂ fluxes ranged from - 0.1 to - 0.25 mg m^–2s^–1.From the data collected over mature soybeans, a relationship between CO₂ flux and photosynthetically active radiation (PAR) was developed. The crop did not appear to be light-saturated at PAR flux densities < 1800 Ei m^–2 s^–1. The light compensation point was found to be about 160 Ei m^–2 s^–1.Published as Paper No. 7402, Journal Series, Nebraska Agricultural Experiment Station. The work reported here was conducted under Nebraska Agricultural Experiment Station Project 27-003 and Regional Research Project 11–33.Post-doctoral Research Associate, Professor and Professor, respectively. Center for Agricultural Meteorology and Climatology, Institute of Agriculture and Natural Resources, University of Nebraska, Lincoln, NE 68583-0728.     

Leaf-level gas exchange and scaling-up of forest understory carbon fixation rates with a “patch-scale” canopy model

Summary During the Hartheim experiment (HartX) 1992, conducted in the Upper Rhine Valley, Germany, we estimated water vapor flux from the understory by several methods as reported in Wedler et al. (this issue). We also examined the photosynthetic gas exchange of the dominant understory speciesBrachypodium pinnatum, Carex alba, andCarex flacca at the leaf level with an CO₂/H₂O porometer. A mechanisticallybased leaf gas exchange model was parameterized for these understory species and validated via the measured diurnal courses of carbon dioxide exchange. Leaf CO₂ gas exchange was scaled-up to patch- and then to stand-level utilizing the leaf gas exchange model as a component of the canopy light interception/energy balance model GAS-FLUX, and by further considering variation in vegetation patch-type distribution, patch-specific spatial structure, patch-type leaf area index, and microclimate beneath the tree canopy.At patch-level,C. alba exhibited the lowest net CO₂ uptake of ca. 75 mmol m^–2 d^–1 due to a low leaf-level photosynthetic capacity, whereas net CO₂ fixation ofB. pinnatum- andC. flacca-patches was approx. 178 and 184 mmol m^–2 d^–1, respectively. Highest CO₂ uptake was estimated for mixed patches whereB. pinnatum grew together with the sedge speciesC. alba orC. flacca. Scaling-up of leaf gas exchange to stand level resulted in an estimated average rate of total CO₂ fixation by the graminoid understory patches of approximately 93 mmol m^–2 d^–1 during the HartX period. The conservative gas exchange behavior ofC. alba at Hartheim and its apparent success in space capture seems to affect overall functioning of this pine forest ecosystem by limiting understory CO₂ uptake. The CO₂ uptake by the understory is approximately 20% of stand total CO₂ uptake. CO₂ uptake fluxes mirror the relative differences in water loss from the understory and crown layer during the HartX period. Comparative measurements indicate that understory vegetation in spruce and pine forests is not greatly different from that of other low-statured natural ecosystems such as tundra or marshes under high light conditions, although CO₂ capture by the understory at Hartheim is at the low extreme of the estimates, apparently due to the success ofC. alba. With 6 Figures     

Flow reactor and triple quadrupole mass spectrometer investigations of negative ion reactions involving nitric acid: Implications for atmospheric HNO3 detection by chemical ionization mass spectrometry

Atmospheric nitric acid measurements by ACIMS (Active Chemical Ionization Mass Spectrometry) are based on ion-molecule reactions of CO₃ ^-(H₂O) _n and NO₃ ^-(H₂O) _n with HNO₃. We have studied these reactions in the laboratory using a flow tube apparatus with mass spectrometric detection of reactant and product ions. Both product ion distributions and rate coefficients were measured. All reactions were investigated in an N₂-buffer (1–3 hPa) at room temperature. The reaction rate coefficients of OH^-, O₂ ^-, O₃ ^-, CO₄ ^-, CO₃ ^-, CO₃ ^-H₂O, NO₃ ^-, and NO₃ ^-H₂O were measured relative to the known rate k=3.0×10^-9 cm³ s^-1 for the reaction of O^- with HNO₃. The main product ion of the reaction of CO₃ ^-H₂O with HNO₃ was found to be (CO₃HNO₃)^- supporting a previous suggestion made on the basis of balloon-borne ACIMS measurements. For the reaction of bare CO₃ ^- with HNO₃ three product ions were observed, namely NO₃ ^-, (NO₃OH)^-, and (CO₃HNO₃)^-. The reaction rate coefficients for CO₃ ^-H₂O (1.7×10^-9 cm³ s^-1) and NO₃ ^-H₂O (1.6×10^-9 cm³ s^-1) were found to be close to the collision rate. The measured k values for bare CO₃ ^- (1.3×10^-9 cm³ s^-1) and NO₃ ^- (0.7×10^-9 cm³ s^-1) are somewhat smaller. The collisional dissociations of CO₃ ^-(H₂O) _n , NO₃ ^-(H₂O) _n (n=1, 2), (CO₃HNO₃)^- and (NO₃HNO₃)^-, occasionally influencing ACIMS measurements, were also studied. Fragment ion distributions were measured using a triple quadrupole mass spectrometer. The results showed that previous stratospheric nitric acid measurements were unimpaired from collisional dissociation processes whereas these processes played a major role during previous tropospheric measurements leading to an underestimation of nitric acid concentrations. Previous ACIMS HNO₃ detection was also affected by the conversion of CO₃ ^-(H₂O) _n to NO₃ ^-(H₂O) _n due to ion source-produced neutral radicals. A novel ACIMS ion source was developed in order to avoid these problems and to improve the ACIMS method.     

A study of the gas-phase reaction of carbonyl fluoride with water

Ab initio molecular orbital calculations are carried out to determine the mechanism and energetics of the homogeneous reaction of carbonyl fluoride, CF₂O, with water, H₂O. The reaction is found to proceed through two chemically activated intermediates: CF₂(OH)₂ and FC(O)OH. These intermediates in the CF₂O+H₂O reaction are suggested to be transient. The CF₂(OH)₂ dissociates to form FC(O)OH and HF, and the FC(O)OH subsequently dissociates to form CO₂ and HF. The net reaction is CF₂O+H₂O 2HF+CO₂     

Turbulent transport of carbon dioxide over a paddy field

Turbulent fluctuations in CO₂ concentrations over a paddy field are measured by a fastresponse device with an open sensing path. This IR device coupled with a sonic anemometer constitutes an eddy correlation instrument to measure CO₂ fluxes. Three experiments were conducted in the surface layer over paddy 90 cm high. The stability (z – d)/L ranged from -0.14 to 0.20, where L denotes the Monin-Obukhov length.CO₂ power spectra show the range of applicability of the -2/3 power law to be between f = 0.2 and f = 2, where f is the frequency normalized by wind speed and height. The cospectral estimate between CO₂ and vertical component of wind speed ranging from f = 0.005 to f = 2 shows a peak at about f = 0.15 under near-neutral stratification.Hourly means of CO₂ flux measured by the eddy correlation method increase with intensity of net radiation. The maximum value of downward flux of CO₂ rises to 0.6 mg cm^-2 hr^-1 over the paddy field at the stage of ear emergence.Some turbulence statistics relating to the CO₂ transport are evaluated: the correlation coefficient between CO₂ and vertical velocity is about -0.3, and that between CO₂ and humidity attains -0.7 ~ -0.8 under unstable stratification; nondimensional gradients _c for CO₂ and _m for wind speed are 0.89 and 0.99, respectively.     

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.     

Shipboard measurements of atmospheric dimethylsulfide and hydrogen sulfide in the Caribbean and Gulf of Mexico

Simultaneous shipboard measurements of atmospheric dimethylsulfide and hydrogen sulfide were made on three cruises in the Gulf of Mexico and the Caribbean. The cruise tracks include both oligotrophic and coastal waters and the air masses sampled include both remote marine air and air masses heavily influenced by terrestrial or coastal inputs. Using samples from two north-south Caribbean transects which are thought to represent remote subtropical Atlantic air, mean concentrations of DMS and H₂S were found to be 57 pptv (74 ng S m^-3, =29 pptv, n=48) and 8.5 pptv (11 ng S m^-3, =5.3 pptv, n=36), respectively. The ranges of measured concentrations for all samples were 0–800 pptv DMS and 0–260 pptv H₂S. Elevated concentrations were found in coastal regions and over some shallow waters. Statistical analysis reveals slight nighttime maxima in the concentrations of both DMS and H₂S in the remote marine atmosphere. The diurnal nature of the H₂S data is only apparent after correcting the measurements for interference due to carbonyl sulfide. Calculations using the measured ratio of H₂S to DMS in remote marine air suggest that the oxidation of H₂S contributes only about 11% to the excess (non-seasalt) sulfate in the marine boundary layer.     

On the scavenging of gaseous nitrogen compounds by large and small rain drops I. A wind tunnel and theoretical study of the uptake and desorption of NH3 in the presence of CO2

An experimental study has been carried out in the Mainz vertical wind tunnel to determine the rate at which NH₃ in the presence of CO₂ is absorbed by freely suspended water drops. The experimental uptake rates were found to be in good agreement with the rates predicted by the Kronig-Brink convective diffusion model and, for gas concentrations in the ppbv range also by the model in which it is assumed that the absorbed gas is well mixed inside the drop (henceforth called well mixed model). The same conclusion was shown to apply also to the desorption of NH₃ from a drop previously exposed to NH₃. The latter result is in contrast to the desorption of SO₂ which must be described by a model which accounts for the diffusion of the species inside the drop. Comparison of our experimental results with theory show further that the uptake of NH₃ in presence of CO₂ is significantly overestimated if the slow reaction CO_2(aq)+H₂OHCO ₃ ^– +H⁺ is neglected in the theoretical computation.     

A theoretical evaluation of water oligomer populations in the Earth's atmosphere

Atmospheric water vapour is treated as an equilibrium mixture of gas-phase water clusters, (H₂O) _i , using recent precise quantum-chemical data on these species. It is shown that within a typical atmospheric temperature/humidity profile, the cluster populations in the Earth's atmosphere decrease with increasing height, being of the order of magnitude of 0.1 mg/m³ and 0.1 g/m³ for the water dimer and trimer, respectively, in the atmospheric pressure region of 700–800 mb.Dedicated to the 50th anniversary of the preparation of the first artificial snow crystal by Prof. Ukitiro Nakaya at the Hokkaido University on 12 March, 1936 (see, e.g., Nakaya et al. (1938)).     

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.     

Biomass burning in the tropical savannas of Ivory Coast: An overview of the field experiment Fire of Savannas (FOS/DECAFE 91)

FOS/DECAFE 91 (Fire of Savannas/Dynamique et Chimie Atmosphérique en Forêt Equatoriale) was the first multidisciplinary experiment organized in Africa to determine gas and aerosol emissions by prescribed savanna fires. The humid savanna of Lamto in Ivory Coast was chosen for its ecological characteristics representative of savannas with a high biomass density (900 g m^–2 dry matter). Moreover the vegetation and the climate of Lamto have been studied for more than twenty years. The emission ratios (X/CO₂) of the carbon compounds (CO₂, CO, NMHC, CH₄, PAH, organic acids and aerosols), nitrogen compounds (NO_x, N₂O, NH₃ and soluble aerosols) and sulfur compounds (SO₂, COS and aerosols) were experimentally determined by ground and aircraft measurements. To perform this experiment, 4 small plots (100×100 m) and 2 large areas (10×10 km) were prepared and burnt in January 1991 during the period of maximum occurrence of fires in this type of savanna. The detailed ecological study shows that the carbon content of the vegetation is constant within 1% (42 g C for 100 g of vegetal dry matter), the nitrogen content (0.29 g N for 100 g of dry matter) may vary by 10% and the sulfur content (0.05 g S/100 d.m.) by 20%. These variations of the biomass chemical content do not constitute an important factor in the variation of the gas and particle emission levels. With the emission ratios characteristic of humid savanna and flaming conditions (CO/CO₂ of 6.1% at the ground and 8% for airborne measurements), we propose a set of new emission factors, taking into account the burning efficiency which is about 80%: 74.4% of the carbon content of the savanna biomass is released to the atmosphere in the form of CO₂, 4.6% as CO, 0.2% as CH₄, 0.5% as NMHC and 0.7% as aerosols. 17.2% of the nitrogen content of the biomass is released as NO_x, 3.5% as N₂O, 0.6% as NH₃ and 0.5% as soluble aerosols.     

Effects of high CO2 levels on surface temperature and atmospheric oxidation state of the early Earth

One-dimensional radiative-convective and photochemical models are used to examine the effects of enhanced CO₂ concentrations on the surface temperature of the early Earth and the composition of the prebiotic atmosphere. Carbon dioxide concentrations of the order of 100–1000 times the present level are required to compensate for an expected solar luminosity decrease of 25–30%, if CO₂ and H₂O were the only greenhouse gases present. The primitive stratosphere was cold and dry, with a maximum H₂O volume mixing ratio of 10^–6. The atmospheric oxidation state was controlled by the balance between volcanic emission of reduced gases, photo-stimulated oxidation of dissolved Fe⁺² in the oceans, escape of hydrogen to space, and rainout of H₂O₂ and H₂CO. At high CO₂ levels, production of hydrogen owing to rainout of H₂O₂ would have kept the H₂ mixing ratio above 2×10^–4 and the ground-level O₂ mixing ratio below 10^–11, even if no other sources of hydrogen were present. Increased solar UV fluxes could have led to small changes in the ground-level mixing ratios of both O₂ and H₂.