A photoelectric detector for the measurement of photolysis frequencies of ozone and other atmospheric molecules

Photoelectric detectors for the measurement of photolysis frequencies of different trace gases in the atmosphere are described. They exhibit uniform response characteristics over one hemisphere (2 sr) and wavelength characteristics closely matched to those of the photolysis frequencies J _O1D, J _NO2, and J _NO3, respectively. Absolute calibration of the J _O1D detector was performed by chemical actinometry with an accuracy of ±16 percent. Simultaneous measurements of J _NO2 and J _O1D are presented.     

The UV-Visible Absorption Cross-Sections and Atmospheric Photolysis Rate of HOI

The UV-visible absorption cross-sections of HOI have been recorded over the wavelength range 278-494 nm and at 298 K following generation of HOI in the gas phase using laser flash photolysis. The gas phase reaction of OH with I₂ was used to produce HOI, and the absorption spectrum of HOI was calibrated relative to the consumption of I₂. The HOI spectrum recorded exhibits 2 broad absorption maxima of = 3.99 × 10^-19 cm² and = 2.85 × 10^-19 cm², centred at 338.4 nm and 404.8 nm respectively. The spectrum is adequately described by a parameterisation consisting of two semi-logarithmic Gaussian distribution functions. The HOI spectrum is more intense than that recorded in previous work of Jenkin, but is in good agreement with more recent work by Bauer et al. The parameterised HOI absorption spectrum recorded in this work was used in a radiative model to calculate the atmospheric photolysis rate (J-value) of HOI. These results indicate that, under most sunlit conditions, HOI has a lifetime with respect to solar photolysis of the order of minutes. Experiments attempting to generate HOI by the reaction of O atoms with C₂H₅I led to complex absorption spectra containing a negative contribution to the absorption from the photolytic removal of an unidentified species. In addition, evidence was found for adsorption and desorption of an iodine-containing species in the reaction vessel. This behaviour is rationalised in terms of the disproportionation of HOI to I₂O, and an uncalibrated spectrum tentatively attributed to I₂O has been recorded.     

Do large-area-average temperature series have an urban warming bias?

Conclusions The arguments presented by Wood and his criticisms of the methods used by Jones et al. are largely fallacious and are generally based on misconceptions and unwarranted assumptions. This does not, of course, mean that the Jones et al. data are perfect. Jones et al. (1986a, b) have clearly stated that, at the regional level, there may be residual uncertainties in their gridded data set. Furthermore, they have noted that there is a residual uncertainty in the global-mean change since late last century of ±0.2 °C (Wigley et al., 1986), although the main reasons for this uncertainty do not relate to urban warming. Further studies of possible urban warming biases are certainly warranted, particularly at the regional scale. However, for averages over continental-scale areas upwards, it is unlikely that any significant urban warming bias remains.     

The influence of isoprene peroxy radical isomerization mechanisms on ozone simulation with the presence of NOx

Isoprene peroxy radical isomerizations (1,5- and 1,6-H shifts) have recently been proposed as important pathways regenerating and recycling HO_x (OH?+?HO₂) in the atmosphere under low-NO_x conditions (Peeters et al. Phys. Chem. Chem. Phys. 28: 5935?C5939 2009; da Silva et al. Environ. Sci. Technol. 44:250?C256 2010). Evaluation and comparison of the isoprene peroxy radical isomerization mechanisms from recent studies have been performed against isoprene-NO_x experiments conducted in the UNC dual outdoor smog chambers. Five different kinetic mechanisms were tested in this study, including the original Master Chemical Mechanism (MCM) v3.1; two modified MCM mechanisms both implementing isoprene peroxy radical isomerization reactions but with different rate coefficients; the Carbon Bond 6 (CB6) mechanism; and the ISO-UNC mechanism. Sensitivity analyses of the unsaturated hydroxyperoxy aldehydes (HPALDs) reaction mechanisms under fast isomerization have also been performed. The results indicate that the fast isomerization mechanism and the mechanisms with high OH yields from HPALDs photolysis both significantly enhance HO_x estimates with increasing isoprene/NO_x ratios. However, O₃ predictions, as well the isoprene decay rates are substantially overestimated. Our results suggest that given the current state of our knowledge, it is difficult to improve both HO_x levels and maintain reasonable O₃ simulations using the Peeters et al. (Peeters et al. Phys. Chem. Chem. Phys. 28: 5935?C5939 2009) mechanism.     

Fluctuations of the horizontal wind under unstable conditions

The similarity relations for _u/u_* proposed by Panofskyet al. (1977) and Højstrup (1982) have been verified using eddy-correlation data collected during the EFEDA-experiment, conducted over the extensive plain of La Mancha (Spain), where vine plants form a primary crop. Also, the standard Monin-Obukhov relation is considered. It is found that the expressions by Panofskyet al. and Højstrup both yield almost identical results, and are better than the Monin-Obukhov expression. Also, _u measured with a cup anemometer obeys the similarity expressions well, provided that the effect of the variation of wind direction on propellor wind speed is accounted for. The relationship of Panofskyet al. works rather well even when the boundary-layer height scaleh is replaced by a fixed height,h _c. Best results were obtained forh _c=1800 m. This height scale is possibly associated with the horizontal variability in the surface sensible heat flux pattern.     

An improved method for integrating the Mixed Spectral Finite Difference (MSFD) model equations

In their Mixed Spectral Finite Difference (MSFD) model for flow over complex terrain, Beljaars et al. (1987) solve a set of coupled, second-order ordinary differential equations (ODEs) for the first-order perturbations to the logarithmic velocity profile caused by nonuniform surface roughness and topography. To solve this set of ODEs, they employ a Forward Euler Shooting Method. It is demonstrated here that the shooting method is computationally unstable for this problem. An absolutely stable finite-difference method based on a block tridiagonal LU factorization of the finite-difference matrix is presented. The advantages of the present algorithm over the method used by Beljaars et al. are demonstrated both by theoretical argument and numerical experiment.     

A reinterpretation of the entrainment process in some laboratory experiments

Pollard et al. (1973) proposed a closure hypothesis for the entrainment process in the stress-mixed layer of a stratified fluid. Some laboratory experiments suitable for testing the hypothesis were carried out by Kantha et al. (1977) and by Kato and Phillips (1969). In the early period of each experiment, before side-wall friction becomes important, these experiments support the closure hypothesis, with a critical Froude number close to 1, perhaps F = 1.2 ± 0.2.     

Estimation of net radiation and surface heat fluxes using NOAA-7 satellite infrared data during fair-weather cloudy situations of Mesogers-84 experiment

Estimation of radiation during fair weather cloudy situations of the MESOGERS-84 experiment has been examined using micrometeorological observations and satellite data. Diurnal variation of cloudiness is empirically determined using satellite information as a function of global radiation, and relationships between net incoming radiation and global radiation are analyzed. Particularly, it has been found that a very simple relationship between global radiation, cloudiness and net radiative heat flux proposed by Nielsenet al. (1981) can be used with satellite data and applied to the Mesogers region in Southwest France. The different relationships between cloudiness and radiation are utilized to modify and to validate Taconet'set al. model (1986) to get fluxes related to a cloudy situation without advection.     

Actinic flux and photolysis frequency comparison computations using the model PHOTOGT

The accurate radiative transfer model GOMETRAN, initially designed to yield radiances at TOA in the wavelength range 240–790 nm, has been extended to allow for the computation of actinic fluxes down to 175 nm and for the calculation of photolysis frequencies in the atmosphere. The capability of the extended model PHOTOGT (PHOTOGOMETRAN) is demonstrated in a number of successful comparison studies both with recent experiments (ground-based, balloonborne, airborne) and model calculations of radiances, actinic fluxes and photolysis frequencies in the stratosphere and troposphere. In an atmospheric case study, the impact of new quantum yield data for the O₃ » O₂+O(¹ d) photodissociation channel on the photolytic production of O(¹ d) atoms in the lower atmosphere has been quantified.     

The effect of gas-phase chemistry on aqueous-phase sulfur dioxide oxidation rates

The rates and mechanisms of both gas and liquid phase reactions for the oxidation of sulfur dioxide play an important role in the production of atmospheric acids and aerosol particles. Rhodeet al. (1981) concluded that sulfate production rates were highly non-linear functions of sulfur dioxide emission rates. Their modelling study used an HO _x termination mechanism for the HO—SO₂ reaction in the gas-phase. Stockwell and Calvert (1983) determined that one of the products of the overall reaction of HO with sulfur dioxide was an HO₂ radical. The National Research Council (1983) using a version of the Rhodeet al. (1981) model modified to include HO₂ production from the HO—SO₂ reaction concluded that sulfate production becomes much more linear with respect to reductions in sulfur dioxide emissions. However, the cause of this increased linearity was not explained by the National Research Council report. It is demonstrated that the increased linearity is due to the coupling of gas-phases and aqueous phase chemistry. The gas-phase sulfur dioxide oxidation mechanism has a very significant effect on hydrogen perodide production rates.     

Stability dependence of the temperature structure parameter

Experimental data of C _T ², determined during various experiments in the surface layer, are compared with several functions giving the stability dependence of the temperature structure parameter. The universal function of the dimensionless temperature gradient by Skeib (1980) follows very well the experimental data and the empirical function by Wyngaard et al. (1971). This function can be used in an inertial-dissipation method.     

Consequences of Uncertainties in CO<Subscript>2</Subscript> Density for Estimating Net Ecosystem CO<Subscript>2</Subscript> Exchange by Open-path Eddy Covariance

Errors in the estimation of CO₂ surface exchange by open-path eddy covariance, introduced during the removal of density terms [Webb et al. Quart J Roy Meteorol Soc 106:85–100, (1980) - WPL], can happen both because of errors in energy fluxes [Liu et al. Boundary-Layer Meteorol 120:65–85, (2006)] but also because of inaccuracies in other terms included in the density corrections, most notably due to measurements of absolute CO₂ density (ρ _c ). Equations are derived to examine the propagation of all errors through the WPL algorithm. For an open-path eddy covariance system operating in the Sierra de Gádor in south-east Spain, examples are presented of the inability of an unattended, open-path infrared gas analyzer (IRGA) to reliably report ρ _c and the need for additional instrumentation to determine calibration corrections. A sensitivity analysis shows that relatively large and systematic errors in net ecosystem exchange (NEE) can result from uncertainties in ρ _c in a semi-arid climate with large sensible heat fluxes (H _s ) and (wet) mineral deposition. When ρ_c is underestimated by 5% due to lens contamination, this implies a 13% overestimation of monthly CO₂ uptake.     

Surface-layer flow in complex terrain: Comparison of models and full-scale observations

Four models of surface boundary-layer flow in complex terrain are compared with observations made at Blashaval Hill, North Uist, Scotland. The field experiment is described by Mason and King (1985). Three of the models are derived from the two-dimensional theory of Jackson and Hunt (1975) and are described in Mason and King (1985), Walmsley et al. (1986) and Troen and Petersen (1989). The fourth is a mass-consistent code based on Traci et al. (1979). The model results are in good agreement with each other and are generally within the observed range of variation ( ~ ± 16%) in normalized wind speed. For most wind direcions (7 of 11), model results of normalized wind speed at the summit were within 7% of the observed mean values. For some wind directions, calculations using the Guidelines of Walmsley et al. (1989) suggested that variations in surface roughness were important. This led us to apply one of our models incorporating nonuniform surface roughness. The lack of significant improvement for cases when water lay upstream of Blashaval Hill is attributed to compensating changes at summit and reference sites and to very local effects on the wind data. Sensitivity to topography lying to the west and northwest of Blashaval was also investigated. Results suggested an influence from those distant topographic features for some wind directions. When those features were incorporated, maximum errors in normalized wind speed at the summit were reduced from 18 to 13%.     

An aircraft study of turbulence dissipation rate and temperature structure function in the unstable marine atmospheric boundary layer

The dissipation rate of turbulent kinetic energy, , and the temperature structure function parameter, C _T ², have been measured over water from the near surface (Z = 3 m) to the top of the boundary layer. The near surface values of and C _T ² were used to calculate the velocity and temperature Monin-Obukhov scaling parameters u _* and T _*. The data collected during unstable lapse rates were used to evaluate the feasibility of extrapolating the values of and C _T ² as a function of height with empirical scaling formulae. The dissipation rate scaling formula of Wyngaard et al. (l971 a) gave a good fit to an average of the data for Z < 0.8 Z _i. In the surface layer the scaling formula of Wyngaard et al. (1971b) disagreed with the C _T ² values by as much as 50%. This disagreement is due to an unexpected reduction in the measured values of C _T ² forZ < 30 m. At this point it is not clear if the discrepancy is a unique property of the marine boundary layer or if it is simply some unknown instrumental or analytical problem. The mixed layer scaling results were similar to the overland results of Kaimal et al. (1976).     

Evidence for zonally-trapped propagating waves in the eastern atlantic from satellite sea surface temperature observations

It has been hypothesized (Moore et al., 1978; O'Brien et al., 1978), that equatorial upwelling and subsequent coastal upwelling on the eastern boundary of the Atlantic Ocean are the result of eastward propagating equatorially trapped Kelvin waves in the Atlantic. Concurrent satellite and ship sea surface temperature observations taken during the GATE experiment permit validation of the satellite data as well as relating sea surface temperature (SST) variability to the local current dynamics. A method based on cross-correlations and cross-spectra of the SST field at various locations is utilized to test the Kelvin wave hypothesis. Significant periodic variation of time lags in the SST variability in the eastern Atlantic is observed by the spectral techniques. Satellite data for the 1974 summer show periodic variability which fits either eastward or westward propagating waves with 1 m s^-1 phase speed, i.e., SST supports the quasi-continuous presence of Kelvin or Yanai waves. We find no evidence for a seasonally solitary eastward propagating signal in the eastern Atlantic from SST.     

Vertical motion diagnostics related to Q-vectors,and the reorganisation of a cold frontal system

Summary Estimates of vertical motion obtained by explicit solution of the quasi-geostrophic omega equation expressed in terms of Q-vectors (Hoskins et al., 1978) were compared with qualitative estimates based on the divergence of Q-vectors. The horizontal distributions of each were broadly similar, but differed in their detail. At any level, the relative magnitudes of centres of vertical motion varied between the parameters. The precise locations of the main centres also differed. Greater differences existed in the vertical distributions of the parameters. The divergence ofQ andF _Q of Hoskins et al. (1978) both reached maximum values in upper levels, whereas peak values of occurred in middle levels. A vertical distribution similar to was achieved ifF _Q was divided by a stability parameter. The diagnosed vertical velocities appeared consistent with the restructuring of a summertime cold front as it crossed waters south of Australia.With 6 Figures     

CO2 feedbacks and the 100 K year cycle in climate

Summary In an earlier paper (Lindzen, 1986), it was shown that allowing CO₂ to vary with snow/sea ice position could lead to a greatly enhanced response in glaciation to 100 K year orbital forcing—even when 20 K year forcing was much stronger. In that model, snow/sea ice position (SSIP) and glaciation were different: the former was the forcing for the latter. However, SSIP and glaciation were not decorrelated. Observations (Berner et al., 1979; Lorius et al., 1985; Neftel et al., 1982) suggest that CO₂ may be independently related to both SSIP and glaciation. In the present paper, we allow (in a highly simplified manner) such independent dependence, and show how it alters the earlier results. Briefly, the dependence of CO₂ on glaciation can contribute to and even cause a highly enhanced response to the 100 K year component of the forcing. However, the CO₂ dependence on SSIP is, on the whole, more effective in this regard. Thus, we expect time series of CO₂ to show variation on the faster time scales than does glaciation.With 5 Figures     

A new method for estimation of near surface specific humidity over global oceans

Summary A new methodology for deriving daily averages of near surface specific humidity (Q _a ) is developed. Remotely sensed parameters, total water vapor (W), boundary-layer water vapor (W _b ), and sea-surface temperature (SST) are used to derive Q _a . Genetic algorithm (GA) is used to find the empirical function relating the input (W, W _b , and SST) and output (Q _a ) parameters. The input data consist of 2 years (1999–2000) of daily W, W _b , from SSM/I (Special Sensor Microwave Imager), and SST data from AVHRR (Advanced Very High Resolution Radiometer). COADS (Comprehensive Ocean Atmospheric Data Set) observations of Q _a are used to develop and evaluate the new methodology. The performance of the algorithm is measured with COADS observations, which are not used in the development phase. The global mean rms error for daily averages Q _a is 1.5 ± 0.40 g/kg. Slightly higher discrepancies between Q _a derived from the new method and COADS observations are found over the Northwestern Pacific, North Atlantic oceans and Arabian Sea. This method improves upon the humidity retrieval of Liu (1986), Schulz et al (1993), and Chou et al (1997).     

Comment: On the need for validation of the Jones et al. temperature trends with respect to urban warming

The Jones et al. hemispheric and global temperature trends and the methodology used to detect and correct for urban heat island effects are examined in detail. The results of this review suggest that there is still the possibility of significant urban warming bias remaining in the hemispheric and global averages. The actual extent of any such bias is unknown but warrants full investigation, since undetected and/or uncorrected urban warming could account for some of the hemispheric and global warming reported by Jones et al. Several research activities are suggested for resolving this uncertainty, including the rigorous application of urban warming correction factors to the data set used by Jones et al. and the development of geographically representative rural temperature series.Office of Technology Assessment, United States Congress, Washington, D.C. 20510, U.S.A. The views expressed are those of the author and not necessarily those of the OTA, Technology Assessment Board, or U.S. Congress. The article is based on independent research of the author and not on work conducted for the OTA.