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.     

In situ Measurement of H2O and CH4 with Telecommunication Laser Diodes in the Lower Stratosphere: Dehydration and Indication of a Tropical Air Intrusion at Mid-Latitudes

Telecommunication laser diodes emitting near 1.39 m and 1.65 m in combination with direct-differential absorption spectroscopy are efficient tools to monitor in situ stratospheric H₂O andCH₄ with a good precision error (a few percents), a high temporal resolution (ranging from 10 ms to 1 s), a large dynamic range in the concentration measurements (four orders of magnitude) and a high selectivity in the analyte species. To illustrate the capability of laser probing technique, we report balloonborne H₂Oand CH₄ simultaneous measurements obtained on October 2001 atmidlatitudes (43° N). The H₂O vertical profile achieved with the lasersensor in the lower stratosphere is compared with the H₂O data yielded by a balloonborne frost-point hygrometer. The total hydrogen mixing ratio in the lower stratosphere, 2[CH₄] + [H₂O], appears to beconstant at 7.5 ± 0.1 ppmv. Nevertheless, an unexpected largedehydration of 0.5 ppmv was detected by both the laser sensor and thehygrometer between 16 km and 23 km. We suspect the occurrence of a tropicalair intrusion into mid-latitudes. We support this interpretation using a high-resolution advection model for potential vorticity.     

An Alternative Approach for CO2 Flux Correction Caused by Heat and Water Vapour Transfer

Energy and CO₂ fluxes are commonly measured above plant canopies using an eddy covariance system that consists of a three-dimensional sonic anemometer and an H₂O/CO₂ infrared gas analyzer. By assuming that the dry air is conserved and inducing mean vertical velocity, Webb et al. (Quart. J. Roy. Meteorol. Soc. 106, 85-100, 1980) obtained two equations to account for density effects due to heat and water vapour transfer on H₂O/CO₂ fluxes. In this paper, directly starting with physical consideration of air-parcel expansion/compression, we derive two alternative equations to correct for these effects that do not require the assumption that dry air is conserved and the use of the mean vertical velocity. We then applied these equations to eddy flux observations from a black spruce forest in interior Alaska during the summer of 2002. In this ecosystem, the equations developed here led to increased estimates of CO₂ uptake by the vegetation during the day (up to about 20%), and decreased estimates of CO₂ respiration by the ecosystem during the night (approximately 4%) as compared with estimates obtained using the Webb et al. approach.     

Methane,carbon monoxide and light non-methane hydrocarbon emissions from African savanna burnings during the FOS/DECAFE experiment

Atmospheric samples from savanna burnings were collected in the Ivory Coast during two campaigns in January 1989 and January 1991. About 30 nonmethane hydrocarbons from C₂ to C₆, carbon monoxide, carbon dioxide and methane were measured from the background and also at various distances from the burning. Concentrations in the fire plume reached ppmv levels for C₂-C₄ hydrocarbons, and 5300, 500 and 93 ppmv for CO₂, CO and CH₄ respectively. The excess in the mixing ratios of these gases above their background level is used to derive emission factors relative to CO and CO₂. For the samples collected immediately in the fire plume, a differentiation between high and low combustion efficiency conditions is made by considering the CO/CO₂ ratio. Ethene (C₂H₄), acetylene (C₂H₂), ethane (C₂H₆) and propene (C₃H₆) are the major NMHC produced in the flaming stage, whereas a different pattern with an increasing contribution of alkanes is observed in samples typical of post flaming processes. A strong correlation between methane and carbon monoxide suggests that these compounds are produced during the same stage of the combustion. In samples collected at a distance from the fire and integrated over a period of 30 minutes, the composition is very similar to that of flaming. NMHC/CO₂ is of the order of 0.7%, CH₄/CO₂ of the order of 0.4% and CO/CO₂ of the order of 6.3%. From this study, a global production by African savanna fires is derived: 65 Tg of CO-C, 4.2 Tg of CH₄-C and 6.7 Tg of NMHC-C. Whereas acetylene can be used as a conservative tracer of the fire plumes, only ethene, propene and butenes can be considered in terms of their direct photochemical impact.     

Methane emission from West Siberian forest-steppe and subtaiga reed fens

Methane emission from West Siberian forest-steppe and subtaiga reed fens (that is, fens dominated by Phragmites australis) observed in summer 2013, is considered using the static chamber method. The obtained medians of CH₄ fluxes varied from -0.08 to 2.7 mg CH₄/m² per hour. Eenvironmental factors affecting methane emission are analyzed. It was found that CH₄ emissions from the reed fens correlate only with the concentration of salt ions in the wetland water and with the plant community structure. The latter probably also depends on water salinity. It was revealed that in fens the ratio between fluxes of CH₄ and CO₂ does not depend on the water table level that contradicts the general pattern simulated by mathematical models of CH₄ emission. It was found that Phragmites australis fens and similar ecosystems should be considered as a separate wetland class from the point of view of methane emission study.     

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     

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.     

A comparison of airborne eddy correlation and bulk aerodynamic methods for ocean-air turbulent fluxes during cold-air outbreaks

Four bulk schemes (LKB, FG, D and DB), with the flux-profile relationships of Liuet al. (1979), Francey and Garratt (1981), Dyer (1974), and Dyer and Bradley (1982), are derived from the viscous interfacial-sublayer model of Liuet al. These schemes, with stability-dependent transfer coefficients, are then tested against the eddy-correlation fluxes measured at the 50 m flight level above the western Atlantic Ocean during cold-air outbreaks. The bulk fluxes of momentum (), sensible heat (H), and latent heat (E) are found to increase with various von Kármán constants (k _M for k _H forH, andk _E forE). Except that the LKB scheme overestimates by 28% (46Wm^–2), on the average, the fluxes estimated by the four bulk schemes appear to be in fairly good agreement with those of the eddy correlation method (magnitudes of biases within 10% for , 17% forH, and 13% forE). The results suggest that the overall fluxes and surface-layer scaling parameters are best estimated by FG and thatk _H <k _E . On the average, the FG scheme underestimates by 10% (0.032N m^–2) andE by 4% (12Wm^–2), and overestimatesH by 0.3% (0.5W m^–2). The equivalent neutral transfer coefficients at 10 m height of the FG scheme compare well with some schemes of those tested by Blanc (1985).The relative importance of various von Kármán constants, dimensionless gradients and roughness lengths to the oceanic transfer coefficients is assessed. The dependence of transfer coefficients on wind speeds and roughness lengths is discussed. The transfer coefficients for andE agree excellently between LKB and FG. However, the ratio of the coefficient forH of LKB to that of FG, increasing with decreasing stability, is very sensitive to stability at low winds, but approaches the neutral value of 1.25 at high winds.     

Experimental investigations into variations of ground-based inversions and comparisons with results of simple boundary-layer models

Meteorological data obtained from sensors mounted on a 300-m antenna mast, including wind components and temperature fluctuations together with high resolution profile measurements, were used to calculate quantities which describe the most important processes during the development and decay of ground-based inversions. The vertical distribution of air temperature during the developing phase of radiation inversions has been measured continuously and compared with an existing simple prognostic model. Free and forced convection conditions have been investigated for the inversion lifting phase by measuring the heat fluxes at the surface (H _s) and at the inversion base (H _i), the heating rate of the mixed layer (/z) _m , the friction velocity (u _*) and the entrainment rate (dh/dt). Comparisons between the directly measured entrainment rates and those calculated by models show good agreement. For nearly free convection conditions, the entrainment parameter (k = -H _i/H_s) has been determined to be about 0.25.     

An open path,fast response infrared absorption gas analyzer for H2O and CO2

An open path infrared absorption based instrument for fast response measurements of H₂O and CO₂ fluctuations is described. This instrument performed reliably in several field experiments in both terrestrial and marine environments, on both fixed (tower) and mobile (boat, plane) flux platforms. Noise levels for H₂O and CO₂ concentrations were less than 10 mg/m³ and 300 g/m³, respectively for frequencies between 0.005 and 10 Hz. Drifts in instrument output, associated with changes in instrument temperature, are compensated for electronically.     

Flux determination over a smooth surface under strongly unstable conditions

Careful micrometeorological measurements on an empty parking lot allowed determination of the surface fluxes of sensible heatH and of momentum by applying profile equations derived from Monin-Obukhov similarity theory with two sets of the stability correction function for momentum _m and sensible heat _h . These fluxes were compared with reference values ofH independently determined by means of an eddy correlation technique. In general, better agreement was found betweenH values derived from profiles with the stability functions of Brutsaert (1992) and referenceH values, than when the Businger-Dyer functions were used to deriveH. The disagreement in the latter comparison was especially serious under strongly unstable conditions, with the value ofy=–z/L (wherez is the height andL is the Obukhov length) larger than 10. A closer look at the procedure for calculatingH from the profiles revealed that the large differences between theH values derived with these two different versions of the stability correction functions were caused by the small differences of the _h values, and not by the larger differences of the _m values. This result stems from the strong sensitivity of the resultingH values on the choice of _h .     

A reliable and efficient two-stream algorithm for spherical radiative transfer: Documentation of accuracy in realistic layered media

We present a fast and well documented two-stream algorithm for radiative transfer and particle transport in vertically inhomogeneous, layered media. The physical processes considered are internal production (emission), scattering, absorption, and Lambertian reflection at the lower boundary. The medium may be forced by internal sources as well as by parallel or uniform incidence at the top boundary. This two-stream algorithm is based on a general purpose multi-stream discrete ordinate algorithm released previously. It incorporates all the advanced features of this well-tested and unconditionally stable algorithm, and includes two new features: (i) corrections for spherical geometry, and (ii) an efficient treatment of internal sources that vary rapidly with depth. It may be used to compute fluxes, flux divergences and mean intensities (actinic fluxes) at any depth in the medium. We have used the numerical code to investigate the accuracy of the two-stream approximation in vertically inhomogeneous media. In particular, computations of photodissociation and warming/cooling rates and surface fluxes of ultraviolet and visible radiation for clear, cloudy and aerosol-loaded atmospheres are presented and compared with results from multi-stream computations. The O₃ +hv O(¹D) + O₂ and O₃ +hv O(³P) + O₂ photodissociation rates were considered for solar zenith angles between 0.0–70.0° and surface albedos in the range 0.0–1.0. For small and moderate values of the solar zenith angle and the surface albedo the error made by the two-stream approximation is generally smaller, <10%, than the combined uncertainty in cross sections and quantum yields. Surface ultraviolet and visible fluxes were calculated for the same range of solar zenith angles and surface albedos as the photodissociation rates. It was found that surface ultraviolet and visible fluxes may be calculated by the two-stream approximation with 10% error or less for solar zenith angles less than 60.0° and surface albedos less than 0.5. For large solar zenith angles and/or large surface albedos, conditions typical at high latitudes, the error made by the two-stream approximation may become appreciable, i.e. 20% or more for the photodissociation rates in the lower stratosphere and for ultraviolet and visible surface fluxes for large surface albedos. The two-stream approximation agrees well with multi-stream results for computation of warming/cooling rates except for layers containing cloud and aerosol particles where errors up to 10% may occur. The numerical code provides a fast, well-tested and robust two-stream radiative transfer program that can be used as a software tool by aeronomers, atmospheric physicists and chemists, climate modellers, meteorologists, photobiologists and others concerned with radiation or particle transport problems. Copies of the FORTRAN77 program are available to interested users.     

Modelling Vegetation-Atmosphere Co2 Exchange By A Coupled Eulerian-Langrangian Approach

A Eulerian-Lagrangian canopy microclimate model wasdeveloped with the aim of discerning physical frombiophysical controls of CO₂ and H₂O fluxes. The model couples radiation attenuation with mass,energy, and momentum exchange at different canopylevels. A unique feature of the model is its abilityto combine higher order Eulerian closure approachesthat compute velocity statistics with Lagrangianscalar dispersion approaches within the canopy volume. Explicit accounting for within-canopy CO₂,H₂O, and heat storage is resolved by consideringnon-steadiness in mean scalar concentration andtemperature. A seven-day experiment was conducted inAugust 1998 to investigate whether the proposedmodel can reproduce temporal evolution of scalar(CO₂, H₂O and heat) fluxes, sources andsinks, and concentration profiles within and above auniform 15-year old pine forest. The modelreproduced well the measured depth-averaged canopy surfacetemperature, CO₂ and H₂O concentrationprofiles within the canopy volume, CO₂ storageflux, net radiation above the canopy, and heat andmass fluxes above the canopy, as well as the velocitystatistics near the canopy-atmosphere interface. Implications for scaling measured leaf-levelbiophysical functions to ecosystem scale are alsodiscussed.     

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).     

In the Core of the Night-Effects of Intermittent Mixing on a Horizontally Heterogeneous Surface

Intermittent breakdowns that accompany wind gusts at the surface are responsible for a large fraction of the turbulent exchange between the surface and the upper boundary layer in the core of clear nights. Vertical and horizontal structure of the breakdowns are investigated using data from a network of 26 stations in an area of 30 km × 30 km. Surface heterogeneity in the area includes complex terrain with different types of land cover. We treat the fine-scale landscape structure near sensors (sheltering) as a separate component of heterogeneity. These features have important consequences on the spatial distribution of mean variables and surface fluxes. We found that breakdowns connect the surface layer to a higher level (level H_C). Weak wind gusts below a threshold (approximately 1.5 m s^-1) mix the air down to the colder ground, cooling the surface layer. On the other hand, wind gusts above this threshold promote mixing with upper levels, warming the surface layer. The spatial maximum of surface temperature over the network can be used as an estimate of the temperature at H_C, allowing vertical gradients and stability to be approximated. Minimum temperature is a function of topography and sheltering. Appreciable surface fluxes at night occur primarily at high, open locations, and can be large enough there to influencearea-averaged values. Surface-fluxparameterizations currently used in mesoscale models were tested first by estimating fluxes at each station and aggregating, and then by formingarea-averages before estimating fluxes. Results show that these formulations underestimate the average surface fluxes over a region for most of the nights.     

Stability Effects on Heat and Moisture Fluxes at Sea

During the 1996 ASGAMAGE experiment we measured windspeed, air temperature T_a, watertemperature T_s, humidity and the momentum,heat and moisture fluxes at a research platform offthe Dutch coast. For each quantity we used several(sets of) instruments simultaneously. This allowed usto make an extensive assessment of the quality of themeasurements and to find optimal values for thevarious quantities for each run. From these values wecalculated C_H and C_E, theStanton and Dalton numbers, and reduced them to 10-mheight and neutral conditions. For this reductionwe made a separate analysis for the effect ofinclusion or non-inclusion of the assumption that theroughness length for heat or moisture is the same forthe neutral and non-neutral cases. Differences inthe reduced data due to this assumption turned out tobe well within the measurement error.For C_H we distinguished three separategroups of data: stable (A), unstable with_{a s} (B) and unstablewith thetas;_a > _s (C), with indicating the potential temperature.The stable data separate into two groups, depending onwater temperature and/or the wave field. The data ofgroup B showed a relation with wave age. The data ofgroup C consistently gave negative values forC_H, a result that might indicate conversion oflatent heat into sensible heat through condensation ofwater vapour just above the water surface. An attemptto re-analyse the data in terms of density fluxes,combining the effects of heat and moisture, still gavenegative transfer coefficients for group C.For the moisture flux we found the more conventionalresult of a separation in stable and unstable values;these categories showed a clear difference, but notrends with, for example, wind speed.We conclude that standard Monin-Obukhov similaritytheory cannot explain our data.     

Limitations of an eddy-correlation technique for the determination of the carbon dioxide and sensible heat fluxes

A modified infrared CO₂ gas analyzer, a small thermocouple assembly, a heated-thermocouple anemometer for horizontal wind, and a propeller-type vertical wind sensor were used to measure the eddy fluxes of heat and CO₂ above a corn crop. Experimental results of these fluxes are discussed. The main sources of errors of the eddy fluxes using these instruments were estimated:

1. Sensors with a time constant of 0.5 s appear to be fast enough to detect most of the vertical CO₂ transfer as long as the sensors are located at least one meter above the crop surface.
2. The deviation from steady-state conditions for 10-min periods was found to have a significant effect on the eddy flux estimates.
3. Temperature fluctuations of the air sample passing through the CO₂ infrared gas analyzer were found to be non-negligible but could be easily corrected.
4. A 1° misalignment of the vertical anemometer affected these eddy fluxes by less than 10% under all circumstances studied.

     

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.     

Ejective and Sweeping Motions Above a Peatland and Their Role in Relaxed-Eddy-Accumulation Measurements and Turbulent Transport Modelling

The three turbulent velocity components, water vapour (\(\text {H}_2\text {O}\)), carbon dioxide (\(\text {CO}_{2}\)), and methane (\(\text {CH}_{4}\)) concentration fluctuations are measured above a boreal peatland and analyzed using conditional sampling and quadrant analysis. The overarching question to be addressed is to what degree lower-order cumulant expansion methods describe transport efficiency and the relative importance of ejections and sweeps to momentum, \(\text {CH}_{4}\), \(\text {CO}_{2}\) and \(\text {H}_2\text {O}\) fluxes across a range of atmospheric flow regimes. The patchy peatland surface creates distinctly different source and sink distributions for the three scalars in space and time thereby adding to the uniqueness of the set-up. The measured and modelled fractional contributions to the momentum flux show that sweep events dominate over ejections in agreement with prior studies conducted in the roughness sublayer. For scalar fluxes, ejections dominate the turbulent fluxes over sweeps. While ejective motions persist longer for momentum transport, sweeping events persist longer for all three scalars. Third-order cumulant expansions describe many of the results detailed above, and the results are surprising given the highly non-Gaussian distribution of \(\text {CH}_{4}\) turbulent fluctuations. Connections between the asymmetric contributions of sweeps and ejections and the flux-transport term arising in scalar turbulent-flux-budget closure are derived and shown to agree reasonably well with measurements. The proposed model derived here is much simpler than prior structural models used to describe laboratory experiments. Implications of such asymmetric contributions on, (i) the usage of the now proliferating relaxed-eddy-accumulation method in turbulent flux measurements, (ii) the constant-flux assumption, and (iii) gradient-diffusion closure models are presented.