Synergistic Effects of Nitrogen Amendments and Ethylene on Atmospheric Methane Uptake under a Temperate Old-growth Forest

An increase in atmospheric nitrogen (N) deposition can promote soil acidification, which may increase the release of ethylene (C2H4) under forest floors. Unfortunately, knowledge of whether increasing N deposition and C2H4 releases have synergistic effects on soil methane (CH4) uptake is limited and certainly deserves to be examined. We conducted some field measurements and laboratory experiments to examine this issue. The addition of (NH4)2SO4 or NH4Cl at a rate of 45 kg N ha-1 yr-1 reduced the soil CH4 uptake under a temperate old-growth forest in northeast China, and there were synergistic effects of N amendments in the presence of C2H4 concentrations equal to atmospheric CH4 concentration on the soil CH4 uptake, particularly in the NH4Cl-treated plots. Effective concentrations of added C2H4 on the soil CH4 uptake were smaller in NH+4 -treated plots than in KNO3-treated plots. The concentration of ca 0.3 μl C2H4 L-1 in the headspace gases reduced by 20% soil atmospheric CH4 uptake in the NH4Cl-treated plots, and this concentration was easily produced in temperate forest topsoils under short-term anoxic conditions. Together with short-term stimulating effects of N amendments and soil acidification on C2H4 production from forest soils, our observations suggest that knowledge of synergistic effects of NH+4 , rather than NO3- , amendments and C2H4 on the in situ soil CH4 uptake is critical for understanding the role of atmospheric N deposition and cycling of C2H4 under forest floors in reducing global atmospheric CH4 uptake by forests. Synergistic functions of NH4+ -N deposition and C2H4 release due to soil acidification in reducing atmospheric CH4 uptake by forests are discussed.     

Chemistry of organic traces in air

The occurrence of CH₂Br₂, CH₂BrCl, CH₂I₂, CH₂ClI, CHBr₃, CHBr₂Cl, CHBrCl₂ and CH₂Br-CH₂Br in marine air and seawater from various sampling sites in the region of the Atlantic Ocean have been measured and evaluated. A correlation exists between high concentrations of these compounds in air and in water and the occurrence of algae at the coastlines of various islands (The Azores, Bermuda, Tenerife) and in a region of high bioactivity in the Atlantic Ocean near the West African coast.Real-world air-water concentration ratios derived from measurements in the open ocean identify the water mass near the African coast with its high primary production as a source for the above compounds. This region has to be discussed also as a possible secondary source in which CHBr₂Cl, CHBrCl₂ and CH₂ClI can be formed via halogen-exchange. Whether CHBrCl₂ and CH₂ClI under-go transformation to CHCl₃ and CH₂Cl₂, respectively, is open to further investigations.Direct photolysis and degradation by OH-radicals lead to a gradient in the marine troposphere with reduced concentrations for the organobromides above the tropospheric boundary layer.Partly presented at: 2nd International Symposium on Biosphere-Atmosphere Exchange, Mainz, F.R.Germany, 16–21 March, 1986. Part VII: Chemosphere 15 (1986) 429–436.     

Model analysis of the measured concentration of organic gases in the Norwegian Arctic

A 2-D meridional model for the chemistry and transport in the troposphere is used to study the seasonal variation of the concentration of organic gases like C₂H₂, C₂H₆, C₃H₈, C₆H₆, C₇H₈. CHCl₃ and C₂Cl₄ at high latitudes. The anthropogenic sources for these species were estimated, and the temporal and latitudinal distribution of OH and O₃ was calculated using a complex photochemical reaction system. There is fair agreement between the calculated annual variation and the measured concentrations for C₂H₂, C₂H₆, C₃H₈, C₇H₈ and C₂Cl₄ at Spitsbergen during July 1982 and March/April 1983, with a distinct late winter maximum and summer minimum. For CHCl₃, the direct anthropogenic source is minor compared to indirect anthropogenic or natural sources. For benzene, emission in car exhaust is important, but other anthropogenic sources are required for the calculations to agree with the measurements. Measured C₂H₄ and C₃H₆ concentrations are much higher than the calculated ones based on anthropogenic emissions, and show opposite seasonal trends. This indicates biogenic sources for these compounds.A buildup of PAN (300 pptv) is calculated at high latitudes during winter. This makes it the dominant source for NO_x as the temperature increases in the spring. NO_x is found to be a limiting factor for O₃ production at high latitudes during spring.     

A nocturnal atmospheric loss of CH<Subscript>2</Subscript>I<Subscript>2</Subscript> in the remote marine boundary layer

Ocean emissions of inorganic and organic iodine compounds drive the biogeochemical cycle of iodine and produce reactive ozone-destroying iodine radicals that influence the oxidizing capacity of the atmosphere. Di-iodomethane (CH₂I₂) and chloro-iodomethane (CH₂ICl) are the two most important organic iodine precursors in the marine boundary layer. Ship-borne measurements made during the TORERO (Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOC) field campaign in the east tropical Pacific Ocean in January/February 2012 revealed strong diurnal cycles of CH₂I₂ and CH₂ICl in air and of CH₂I₂ in seawater. Both compounds are known to undergo rapid photolysis during the day, but models assume no night-time atmospheric losses. Surprisingly, the diurnal cycle of CH₂I₂ was lower in amplitude than that of CH₂ICl, despite its faster photolysis rate. We speculate that night-time loss of CH₂I₂ occurs due to reaction with NO₃ radicals. Indirect results from a laboratory study under ambient atmospheric boundary layer conditions indicate a k _CH2I2+NO3 of ≤4 × 10^?13 cm³ molecule^?1 s^?1; a previous kinetic study carried out at ≤100 Torr found k _CH2I2+NO3 of 4 × 10^?13 cm³ molecule^?1 s^?1. Using the 1-dimensional atmospheric THAMO model driven by sea-air fluxes calculated from the seawater and air measurements (averaging 1.8 +/? 0.8 nmol m^?2 d^?1 for CH₂I₂ and 3.7 +/? 0.8 nmol m^?2 d^?1 for CH₂ICl), we show that the model overestimates night-time CH₂I₂ by >60 % but reaches good agreement with the measurements when the CH₂I₂ + NO₃ reaction is included at 2–4 × 10^?13 cm³ molecule^?1 s^?1. We conclude that the reaction has a significant effect on CH₂I₂ and helps reconcile observed and modeled concentrations. We recommend further direct measurements of this reaction under atmospheric conditions, including of product branching ratios.     

Total column densities of tropospheric and stratospheric trace gases in the undisturbed Arctic summer atmosphere

Ground-based FTIR measurements have been performed in the Arctic summer in July 1993 and June 1994 at 79° N to study the zenith column densities of several trace gases in the undisturbed Arctic summer atmosphere. Zenith column densities of H₂O, N₂O, HNO₃, NO₂, NO, ClONO₂, ClO, HCl, HF, COF₂, OCS, SF₆, HCN, CH₄, C₂H₆, C₂H₂, CO, O₃, CFC-12, CFC-22, and CO₂ were retrieved by line-by-line calculations. The results are compared with winter and springtime observations measured at the same site, with column densities obtained in the Antarctic summer atmosphere, and with measurements at midlatitudes. For HCl the spectra give lower total zenith columns than expected, but the ratio HF/HCl agrees well with midlatitude literature data. Measurements of ClONO₂ give low total columns in agreement with observations at midlatitudes. In the undisturbed atmosphere HCl was found to be in excess of ClONO₂. The total columns of HNO₃, N₂O and the sum of NO and NO₂ agree with summer observations in Antarctica. Results for the tropospheric trace gas C₂H₆ are higher by 250% when compared with Antarctic observations. Contrary to N₂O and CH₄ the seasonal cycle of C₂H₆ and C₂H₂ give much higher total columns in winter/spring compared to the summer observations. This is assigned to transport of polluted airmasses from mid-latitudes into the Arctic.     

Relations between Light Hydrocarbon, Carbon Monoxide, and Carbon Dioxide Concentrations in the Plume from the Combustion of Plant Material in a Furnace

To systematically explain relations between light hydrocarbons, CO, and CO₂ concentrations/emissions of biomassburning, we measured concentrations/emissions of carbon gases – CO,CO₂, light hydrocarbons (CH₄, C₂H₆,C₂H₄, C₂H₂, C₃H₈, C₃H₆,n-C₄H₁₀, i-C₄H₁₀, n-C₅H₁₂,i-C₅H₁₂), and THC (total hydrocarbon) – in the burning of dead plant material, mainly Imperata grass, byclosed-chamber experiments and by time-series analyses of gas concentrations in combustion plumes in relatively efficient and inefficient combustion situations. Concentrations of hydrocarbons measured were well correlated to [CO] although [C₂H₂] was exceptionally well correlated to[CO₂]. The phase diagrams (relation between [CO]/ [CO₂] and [hydrocarbon]/ [CO₂]) obtained by the time-seriesexperiments well illustrated the variation in the overall emission rates of the closed-chamber experiments. The higher rates of decrease in hydrocarbon concentration with increasing carbon number in the efficient case compared with the inefficient case probably reflected the rate of oxidation and the amount of radicals. The overall concentrations (or emissions) of C₂H₄ and C₃H₆ were higher thanthose of C₂H₆ and C₃H₈, suggesting a linkage to mechanisms in whichthe predominant path of hydrocarbon oxidation is through the degradation of alkyl radicals, which can be immediately converted into or formed from alkenes. For C₃ and C₄ species, normal-chain species hadhigher emissions than iso-chain species under lower combustion efficiency. This may be attributable to the presence of tertiary C–H bonds in iso-species,which show more reactivity in the abstraction of H than secondary C–H bonds unless the carbon number is large.     

The measurement of natural sulfur emissions from soils and vegetation: Three sites in the Eastern United States revisited

Sulfur fluxes from bare soils, naturally vegetated surfaces and from several agricultural crops were measured at two mid-continent sites (Ames, Iowa and Celeryville, Ohio) and from one salt water marsh site (Cedar Island, North Carolina) during a field program conducted jointly by the NOAA Aeronomy Laboratory, Washington State University Laboratory for Atmospheric Research and University of Idaho Department of Chemistry during July and August 1985. The sites were chosen specifically because they had been characterized by previous studies (Anejaet al., 1979; Adamset al., 1980, 1981). The NOAA gas chromatographic/dynamic-enclosure measurements yielded bare soil surfaces fluxes from the mid-continent sites composed predominantly of COS, H₂S, CH₃–S–CH₃ (DMS) and CS₂, all of which were strongly correlated with air temperature. Net fluxes of approximately 5 and 15 ng S/m² min were observed in Iowa and Ohio, respectively, at appropriate weighted mean July temperatures. These fluxes are roughly a factor of 10 smaller than the earlier measurements, the greatest difference being in the measurement of the H₂S flux. The presence of growing vegetation was observed to measurably increase the flux of H₂S, significantly increase that of DMS and to decrease that of COS. Sulfur fluxes in the Cedar Island environs were observed to be both spatially and temporally much more variable and to include CH₃SH as a measurable contributor. Net fluxes, composed predominantly of DMS and H₂S, were estimated to be about 300 ngS/m²min during August; again about a factor of 10 lower than previous estimates. All measurements were corroborated to within about a factor of 2 by those of the other participating laboratories.     

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.     

Carboxylic monoacids in the air of mayombe forest (Congo): Role of the forest as a source or sink

In the tropical rain forests of the Congo during the dry season, from June to September 1987, carboxylic acid partial pressures (P _gas) in the air above the canopy, at ground level, and at the boundary layer, were estimated from water samples such as fog and rainwater. The concentrations of these acids were also measured in the sap of tree leaves. Tree leaves act as a sink or as a source if the acid P _gas is greater of lower than the acid concentrations in molecular form in sap. For each of these soluble gases, there is a value of P _gas where the exchange is nul. This is called the compensation point. Values of the compensation point for some tree leaves were evaluated according to Henry's law. Henry's law coefficients at ppm levels were redetermined for formic (HCOOH), acetic (CH₃COOH), propionic (CH₃CH₂COOH), and isobutyric (CH₃CH(CH₃)COOH) acids.By comparison of P _gas and compensation points, it is concluded that the forest was a potential source for these acids. The soil-or the litter-acts as a significant source of a carboxylic acid of C₃ or C₄ atoms in the aliphatic chain. This carboxylic acid, not yet fully characterized, could play an important role in the rain acidity in forested zones of the equatorial areas.The direct emission of these carboxylic acids by vegetation was the main source in the boundary layer above the forest. The average emissions were 3.1×10⁹, 7.8×10⁹, and 8.4×10⁹ molecules cm^-2 s^-1 for HCOOH, CH₃COOH, and CH₃CH₂COOH, respectively. The savanna is an exogenous source of HCOOH and CH₃CH₂COOH during moderately rainy days for 30% of the time. The ozonolysis of isoprene seems to be a small source of HCOOH.     

The role of clouds in tropospheric photochemistry

We show that photochemical processes in the lower half of the troposphere are strongly affected by the presence of liquid water clouds. Especially CH₂O, an important intermediate of CH₄ (and of other hydrocarbon) oxidation, is subject to enhanced breakdown in the aqueous phase. This reduces the formation of HO _x -radicals via photodissociation of CH₂O in the gas phase. In the droplets, the hydrated form of CH₂O, its oxidation product HCO₂ ^–, and H₂O₂ recycle O₂ ^– radicals which, in turn, react with ozone. We show that the latter reaction is a significant sink for O₃. Further O₃ concentrations are reduced as a result of decreased formation of O₃ during periods with clouds. Additionally, NO _x , which acts as a catalyst in the photochemical formation of O₃, is depleted by clouds during the night via scavenging of N₂O₅. This significantly reduces NO _x -concentrations during subsequent daylight hours, so that less NO _x is available for O₃ production. Clouds thus directly reduce the concentrations of O₃, CH₂O, NO _x , and HO _x . Indirectly, this also affects the budgets of other trace gases, such as H₂O₂, CO, and H₂.     

Influence of the surface microlayer on the flux of nonconservative trace gases (CO,H2, CH4, N2O) across the ocean-atmosphere interface

Gas exchange experiments were conducted in the tropical Atlantic Ocean during a ship expedition with FS Meteor using a small rubber raft. The temporal change of the mixing ratios of CO, H₂, CH₄ and N₂O in the headspace of a floating glass box and the concentrations of these gases in the water phase were measured to determine their transfer velocities across the ocean-atmosphere interface. The ocean acted as a sink for these gases when the water was undersaturated with respect to the mixing ratio in the headspace. The transfer velocities were different for the individual gases and showed still large differences even when normalized for diffusivity. Applying the laminar film model, film thicknesses of 20 to 70 m were calculated for the observed flux rates of the different gas species. When the water was supersaturated with respect to atmospheric CO, H₂, CH₄ and N₂O, the transfer velocities of the emission process were smaller than those determined for the deposition process. In case of H₂ and CH₄, emission was even not calculable although, based on the observed gradient, the laminar film model predicted significant fluxes at the air-sea interface. The results are interpreted by destruction processes active within the surface microlayer.     

Photooxidation of dimethyl sulfide and dimethyl disulfide. II: Mechanism evaluation

The mechanisms for atmospheric photooxidation of CH₃SCH₃ and CH₃SSCH₃ developed in Part I are evaluated by a series of outdoor smog chamber experiments. Measured product yields, including SO₂, H₂SO₄, CH₃SO₃H and HCHO, are reported. The predictions of the mechanisms developed in Part I are found to be in substantial agreement with the measured concentrations from the smog chamber. By comparison of mechanism predictions and observations, critical uncertainties in the mechanism are identified.     

The influence of light intensity,SO2, NOx and C3H6 on sulfate aerosol formation

The photochemical oxidation of SO₂ in the presence of NO and C₃H₆ was studied in a 18.2 liter pyrex reactor. When light intensity, irradiation time and SO₂ concentration were constant, SO₄ ^2- concentration, derived from the total volume of aerosol produced, peaked when [C₃H₆]/[NO] was approximately 6.0. Another increase im SO₄ ^2- formation was reached at very high ratios (>50). The experimental observations are consistent with the two SO₂ oxidation mechanisms. At low [C₃H₆]/[NO] ratios, the processes proceed via the HO–SO₂ reaction, while at high ratios the O₃–C₃H₆ adduct is assumed to oxidize SO₂ to produce SO₄ ^2- aerosols.     

Hydrogen Peroxide, Organic Peroxides and Higher Carbonyl Compounds Determined during the BERLIOZ Campaign

Gas-phase H₂O₂, organic peroxides and carbonyl compoundswere determined at various sites from Mid-July to early August 1998 during the BERLIOZ campaign in Germany. The sites were located northwest of Berlin and were chosen to determine pollutants downwind of the city emissions during a summer smog episode. Hydrogen peroxide (H₂O₂),methyl hydroperoxide (MHP, CH₃OOH) and occasionally hydroxymethyl hydroperoxide (HMHP, HOCH₂OOH) were quantified in air samples by commercial fluorimetric methods and classical HPLC with post-column derivatisation by horseradish peroxidase/p-hydroxyphenyl acetic acid and fluorimetric detection. Carbonyl compounds were determined in ambient air by a novel method based onO-pentafluorobenzyl hydroxylamine as derivatisation agent.Mixing ratio profiles of the hydroperoxides and the carbonyl compounds are reported for the intensive phase of the campaign, 20–21 July, 1998. Peroxides showed pronounced diurnal variations with peak mixing ratios in the early afternoon. At times, a second maximum was observed in the late afternoon. The major part of the H₂O₂ was formed throughrecombination reactions of HO₂ radicals, but there is some evidencethat H₂O₂ is also formed from ozonolysis ofanthropogenic and/or biogenic alkenes. Diurnal variations of mixing ratios of various carbonyl compounds are reported: alkanals (C₂ to C₁₀,isobutanal), unsaturated carbonyl compounds (methacrolein, methylvinylketone, acrolein), hydroxycarbonyl (glycolaldehyde, hydroxyacetone) and dicarbonyl compounds (glyoxal, methylglyoxal, biacetyl), aromatic compounds (benzaldehyde, o- and m-tolylaldehyde) and pinonaldehyde.     

The Impact of Precipitation Scavenging on the Transport of Trace Gases: A 3-Dimensional Model Sensitivity Study

With the global Chemistry-Transport model MATCHsensitivity simulations were performed to determinethe degree to which especially upward transport ofgases from the earth's surface is limited byconvective and large-scale precipitation scavenging.When only dissolution of species in the liquid phaseis taken into account, mixing ratio reductions in themiddle and upper troposphere by 10% arecalculated for gases with a Henry's Law constant H of10³ mol/l/atm. The removal increases to 50% forH = 10⁴ mol/l/atm, and to 90% for H =10⁵ mol/l/atm. We also consider scavenging by theice phase, which is generally much less efficient thanby the aqueous phase. In fact, rejection of gases fromfreezing water droplets may be a source of trace gasat higher altitudes.H₂O₂ and the strong acids (H₂SO₄,HNO₃, HCl, HBr, HI) have such large solubilitiesthat they become largely removed by precipitation.When significant concentrations of these gases andsulfate aerosol exist above the liquid water domain ofthe atmosphere, they have likely been produced thereor at higher altitudes, although some could have comefrom trace gas rejection from ice particles or fromevaporating hydrometeors. Several other gases areaffected by precipitation, but not strongly enough toprevent fractional transfer to the middle and uppertroposphere: e.g., HNO₄, HNO₂ at pH 5,CH₂O, the organic acids at pH 6,CH₃SOCH₃, HOCl, HOBr, and HOI. NH₃ islargely removed by liquid phase scavenging at pH 7 and SO₂ atpH 7. At pH less thanabout 6, upward transport of SO₂ should largelydepend on the efficiency of oxidation processes in thewater droplets by O₃ and H₂O₂.Most gases have solubilities which are too low forsignificant precipitation scavenging and aqueous phaseoxidation to occur. This holds, e.g., for O₃, CO,the hydrocarbons, NO, NO₂, HCN, CH₃CN,CH₃SCH₃, CH₃O₂H, CH₃CHOandhigher aldehydes, CH₃OH and higher alcohols,peroxyacetylnitrate (PAN), CH₃COCH₃ andother ketones (note that some of these are not listedin Table I because their solubilities are below 10mol/l/atm). Especially for the short-lived gases,transfer from the boundary layer to the middle andupper troposphere is actually promoted by the enhancedupward transport that occurs in clouds.     

Measurements of atmospheric hydroperoxides at a rural site in central Japan

Measurements of hydroperoxides (H₂O₂ and MHP) at ground level were made from 2012 to 2015 in Imizu City, Toyama Prefecture in central Japan. H₂O₂ and MHP concentrations ranged from 0.01 to 3.5 ppb and from below the level of detection (< 0.01 ppb) to 1.4 ppb, respectively. The concentrations of H₂O₂ and MHP were high in the summer and low in the winter. The H₂O₂ concentration was at its maximum in July and August, whereas the concentration of O₃ in the daytime was highest in May and June. The ratio of [H₂O₂]/[SO₂] presented clear seasonal variations. Many cases showed the condition of [H₂O₂] < [SO₂], called oxidant limitation especially in the cold months. Hydroperoxide concentrations in the rainwater were also high in the summer. The concentrations of MHP were much lower than those of H₂O₂ in the rain water. High concentrations of H₂O₂ (> 2.5 ppb) were detected in the summer during the inflow of air pollution. The concentrations of H₂O₂ were significantly high in July and August of 2013. The H₂O₂ was well correlated with the O₃ in July and August whereas there was no correlation between O₃ and H₂O₂ in May and June. There was a negative correlation between NO_X and H₂O₂.     

Identification of Regional Sources of Methyl Bromide and Methyl Iodide from AGAGE Observations at Cape Grim,Tasmania

There are large uncertainties in identifying and quantifying the globally significant sources and sinks of methyl bromide (CH₃Br) and methyl iodide (CH₃I). Long-term, quasi-continuous observations can provide valuable information about their regional sources, which may be significant in the global context. We report 3 years of in situobservations of these trace gases from the AGAGE (Advanced Global Atmospheric Gas Experiment) program at Cape Grim, Tasmania (41 °S, 145 °E). The average background levels of CH₃Br and CH₃I during March 1998–March 2001 were 8.05 and 1.39 ppt (dry air mole fractions expressed in parts per 10¹²), respectively. The CH₃Br background data showed little seasonal variability. Trajectory analyses reveal that air masses showing elevated CH₃Br levels at Cape Grim have had significant contact with coastal-terrestrial and/or coastal-seawater and/or urban source regions. The CH₃I background data showed a seasonal cycle with a 3-year average amplitude of 0.47 ppt and maximum concentrations in summer, suggesting that the Southern Ocean is a significant source.Trajectory analyses reveal that air masses showing highly elevated CH₃I levels at Cape Grim have had significant contact with coastal-terrestrial and/or coastal-seawater regions and/or the open-ocean regions of Bass Strait and the Tasman Sea.     

A theory for the scalar roughness and the scalar transfer coefficients over snow and sea ice

Although the bulk aerodynamic transfer coefficients for sensible (C _H ) and latent (C _E ) heat over snow and sea ice surfaces are necessary for accurately modeling the surface energy budget, they have been measured rarely. This paper, therefore, presents a theoretical model that predicts neutral-stability values of C _H and C _E as functions of the wind speed and a surface roughness parameter. The crux of the model is establishing the interfacial sublayer profiles of the scalars, temperature and water vapor, over aerodynamically smooth and rough surfaces on the basis of a surface-renewal model in which turbulent eddies continually scour the surface, transferring scalar contaminants across the interface by molecular diffusion. Matching these interfacial sublayer profiles with the semi-logarithmic inertial sublayer profiles yields the roughness lengths for temperature and water vapor. When coupled with a model for the drag coefficient over snow and sea ice based on actual measurements, these roughness lengths lead to the transfer coefficients. C _E is always a few percent larger than CH. Both decrease monotonically with increasing wind speed for speeds above 1 m s^–1, and both increase at all wind speeds as the surface gets rougher. Both, nevertheless, are almost always between 1.0 × 10^–3 and 1.5 × 10^–3.     

Analysis of the origins and implications of the18O content of stratospheric water vapor

Factors influencing the¹⁸O content of stratospheric H₂O are reviewed in order to provide a theoretical framework for the interpretation of measurements of this quantity, which are now becoming available. Depletions in¹⁸O of 5–10% in stratospheric H₂O are expected based on the known correlation between that of D and¹⁸O in tropospheric H₂O and observed measurements of large (typically 50%) depletions of D in stratospheric H₂O. H₂O formed in the stratosphere as a result of oxidation of CH₄ can be expected to reflect primarily the¹⁸O content of stratospheric O₂, which is the same as that of tropospheric O₂ (slightly enhanced with respect to standard mean ocean water). Thus, a reduction in the¹⁸O depletion is expected with increasing altitude, but not a large enhancement in¹⁸O in upper stratospheric H₂O as found in recent far infrared measurements. The observed large enhancement of¹⁸O in stratospheric O₃ is not expected to be reflected in stratospheric H₂O. Necessary laboratory data for the improved quantification of these effects are reviewed.