Stable Isotope Ratios: Hurricane Olivia

The oxygen and hydrogen isotopic compositions of rains from HurricaneOlivia (1994) in the eastern Pacific were measured. The rains werecollected on 24 and 25 September during airplane flights conducted at anelevation of 3 km. Hurricane Olivia peaked in intensity to a category-4storm between the two dates. Isotope ratios of rains from HurricaneOlivia were markedly lower ( ¹⁸O = –13.9to –28.8) than that of rain collected from a thunderstormat an elevation of 2.3 km outside the influence of Olivia (¹⁸O = –3.8). A distinct decrease in isotoperatios from the first day to the next ( ¹⁸O =–18.4 to –21.9) in Hurricane Olivia wasattributed to decreased updraft velocities and outflow aloft. Thisshifted the isotopic water mass balance so that fewer hydrometeors werelifted and more ice descended to flight level. A decrease in the averagedeuterium excess from the first day to the next (d = 15.5 to 7.1)was attributed to an increase in the relative humidity of the watervapor `source' area. We hypothesize that the `source' region for therain was in the boundary layer near the storm center and that becausethe hurricane was at peak intensity prior to the second day the relative humidity was higher.     

Isotopic Composition of Non-Methane Hydrocarbons in Emissions from Biomass Burning

The stable carbon isotope ratios of nonmethane hydrocarbons (NMHC) and methyl chloride emitted from biomass burning were determined by analyzing seven whole air samples collected during different phases of the burning process as part of a laboratory study of wood burning. The average of the stable carbon isotope ratios of emitted alkanes, alkenes and aromatic compounds is identical to that of the burnt fuel; more than 50% of the values are within a range of ±1.5 of thecomposition of the burnt fuel wood. Thus for the majority of NMHC emitted from biomass burning stable carbon isotope ratio of the burnt fuel a good first order approximation for the isotopic composition of the emissions. Of the more than twenty compounds we studied, only methyl chloride and ethyne differed in stable carbon isotope ratios by more than a few per mil from the composition of the fuel. Ethyne is enriched in ¹³C by approximately 20–30, and most of the variability can beexplained by a dependence on flame temperature. The ¹³C values decreaseby 0.019 /K (±0.0053/K) with increasing temperature. Methyl chloride is highly depleted in ¹³C, on average by25. However the results cover a wide range of nearly 30. Specifically, in two measurements with wood from Eucalyptus (Eucalyptus delegatensis) as fuel we observed the emission of extremely light methyl chloride (–68.5and–65.5). This coincides with higher than average emission ratiosfor methyl chloride (15.5 × 10^–5 and 18 ×10^–5 mol CH₃Cl/mol CO₂). These high emission ratios are consistent with the highchlorine content of the burnt fuel, although, due to the limited number of measurements, it would be premature to generalize these findings. The limited number of observations also prevents any conclusion on a systematic dependence between chlorine content of the fuel, emission ratios and stable carbon isotope ratio of methyl chloride emissions. However, our results show that a detailed understanding of the emissions of methyl chloride from chloride rich fuels is important for understanding its global budget. It is also evident that the usefulness of stable carbon isotope ratios to constrain the global budget of methyl chloride will be complicated by the very large variability of the stable carbon isotope ratio of biomass burning emissions. Nevertheless, ultimately the large fractionation may provide additional constraints for the contribution of biomass burning emissions to the atmospheric budget of methyl chloride.     

Equatorial disturbances,monsoons, and 1982–1983 ENSO

Summary Interannual modes are described in terms of three-month running mean anomaly winds (u,v), outgoing longwave radiation (OLR), and sea surface temperature (T _* ). Normal atmospheric monsoon circulations are defined by long-term average winds (u _n,v _n) computed every month from January to December. Daily winds are grouped into three frequency bands, i.e., 30–60 day filtered winds (u _L,v _L); 7–20 day filtered winds (u _M,v _M); and 2–6 day filtered winds (u _S,v _S). Three-month running mean anomaly kinetic energy (signified asK _L , K _M , andK _S , respectively) is then introduced as a measure of interannual variation of equatorial disturbance activity. Interestingly, all of theseK _L , K _M , andK _S perturbations propagate slowly eastward with same phase speed (0.3 ms^–1) as ENSO modes. Associated with this eastward propagation is a positive (negative) correlation between interannual disturbance activity (K _L , K _M , K _S ) and interannualu (OLR) modes. Namely, (K _L , K _M , K _S ) becomes more pronounced than usual nearly simultaneously with the arrival of westerlyu and negativeOLR (above normal convection) perturbutions. In these disturbed areas with (K _L , K _M , K _S >0), upper ocean mixing tends to increase, resulting in decreased sea surface temperature, i.e.T _* 0. Thus, groups (not individual) of equatorial disturbances appear to play an important role in determiningT _* variations on interannual time scales. HighestT _* occurs about 3 months prior to the lowestOLR (convection) due primarily to radiational effects. This favors the eastward propagation of ENSO modes. The interannualT _* variations are also controlled by the prevailing monsoonal zonal windsu _n, as well as the zonal advection of sea surface temperature on interannual time scales. Over the central Pacific, all of the above mentioned physical processes contribute to the intensification of eastward propagating ENSO modes. Over the Indian Ocean, on the other hand, some of the physical processes become insignificant, or even compensated for by other processes. This results in less pronounced ENSO modes over the Indian Ocean.With 10 FiguresContribution No. 89-6, Department of Meteorology, University of Hawaii, Honolulu, Hawaii.     

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

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

A preliminary study of the carbon-isotopic content of ambient formic acid and two selected sources: Automobile exhaust and formicine ants

Relatively large quantities (1 mg) of formic acid have been collected from the atmosphere and subjected to carbon-isotopic analysis, as a means of source discrimination. Ambient formic acid was captured on Ca(OH)₂-treated filters using a high-volume sampler. The collection method was not only efficient (>96%), but also appears to have low artifact production.Most of the samples (36 out of 52) were collected over a two-year period at the summit of Mount Lemmon, Arizona, where a strong seasonality in HCOOH mixing ratio was observed (0.2 ppb during winter months to 1.5 ppb in the summer). Other collection sites included the Oregon coast, Colorado Rockies, urban Tucson, and the North Dakota prairie. The carbon-13 content of atmospheric HCOOH was found to be have little variation (–18 to –25), regardless of location or season. This is consistent with a single dominant source of formic acid. The carbon-14 measurements of 6 Mount Lemmon samples showed high levels of modern carbon (93–113% modern).The emissions from formicine ants and automobile combustion were selected as two other potential sources for isotopic analysis. The HCOOH collected from auto exhaust was much more depleted in¹³C than the atmospheric samples, with a ¹³C of –28.0 and –48.6 from a leaded and unleaded automobile, respectively. Formicine ants, on the other hand, ranged from –17.2 to –20.6.     

A study of the sensitivity of bare soil evaporation schemes to soil surface wetness,using the coupled soil moisture and surface temperature prediction model,BARESOIL

Summary The performance of evaporation schemes with and approach and their combination within resistance representation of evaporation from bare soil surface is discussed. For this purpose nine schemes, based on different functions of or , on the ratio of the volumetric soil moisture content and its saturated value are used.The quality of the chosen schemes has been evaluated using the results of time integration by the coupled soil moisture and surface temperature prediction model, BARESOIL, using in situ data. A sensitivity analysis was made using two sets of data derived from the volumetric soil moisture content of the top soil layer. One with values below the wilting point (0.17 m³m^–3) and the second with values above 0.20m³m^–3. Data sets were obtained at the experimental site Rimski anevi, Yugoslavia, from the bare surface of a chernozem soil.With 4 Figures     

Effect of land management on ecosystem carbon fluxes at a subalpine grassland site in the Swiss Alps

Summary The influence of agricultural management on the CO₂ budget of a typical subalpine grassland was investigated at the Swiss CARBOMONT site at Rigi-Seebodenalp (1025m a.s.l.) in Central Switzerland. Eddy covariance flux measurements obtained during the first growing season from the mid of spring until the first snow fall (17 Mai to 25 September 2002) are reported. With respect to the 10-year average 1992–2001, we found that this growing season had started 10 days earlier than normal, but was close to average temperature with above-normal precipitation (100–255% depending on month). Using a footprint model we found that a simple approach using wind direction sectors was adequate to classify our CO₂ fluxes as being controlled by either meadow or pasture. Two significantly different light response curves could be determined: one for periods with external interventions (grass cutting, cattle grazing) and the other for periods without external interventions. Other than this, meadow and pasture were similar, with a net carbon gain of –128±17g Cm^–2 on the undisturbed meadow, and a net carbon loss of 79±17g Cm^–2 on the managed meadow, and 270±24g Cm^–2 on the pasture during 131 days of the growing season, respectively. The grass cut in June reduced the gross CO₂ uptake of the meadow by 50±2% until regrowth of the vegetation. Cattle grazing reduced gross uptake over the whole vegetation period (37±2%), but left respiration at a similar level as observed in the meadow.     

Occurrence of roll circulations in a shallow boundary layer

Meteorological measurements taken at the Näsudden wind turbine site during slightly unstable conditions have been analyzed. The height of the convective boundary layer (CBL) was rather low, varying between 60 and 300 m. Turbulence statistics near the ground followed Monin-Obukhov similarity, whereas the remaining part of the boundary layer can be regarded as a near neutral upper layer. In 55% of the runs, horizontal roll vortices were found. Those were the most unstable runs, with -z _i/L > 5. Spectra and co-spectra are used to identify the structures. Three roll indicators were identified: (i) a low frequency peak in the spectrum of the lateral component at low level; (ii) a corresponding increase in the vertical component at mid-CBL; (iii) a positive covariance {ovvw} together with positive wind shear in the lateral direction (V/z) in the CBL. By applying these indicators, it is possible to show that horizontal roll circulations are likely to be a common phenomenon over the Baltic during late summer and early winter.     

Cape Grim isotope measurements — A preliminary assessment

Measurements of the stable carbon isotope ratio in atmospheric CO₂ permit a distinction between variations resulting from biospheric and oceanic exchange. In situ extraction of CO₂ from Cape Grim air (41°S) for isotopic analysis commenced in 1977; however difficulties with technique reliability were experienced until 1982. Since 1982, 2.6 years of relatively consistent values have accumulated.For a preliminary assessment of the latter data, estimates of the isotopic behaviour from the global transport and inter-reservoir exchange model of Pearman and Hyson (1985) have been employed. The assessment demonstrates the precision requirements of a carbon isotope monitoring program and the relevance of the isotope measurements as a constraint on parameterization of the model.Clear evidence of the changes due to fossil fuel combustion is seen in the year-to-year differences in ¹³C, with the mean and standard error of the overall trend being –0.025±0.005 yr^-1. A significant seasonal variation in ¹³C is apparent, despite considerable inter-annual variability possibly associated with the 1982/83 ENSO phenomena. The average peak-to-peak amplitude is 0.055±0.014 with a maximum on day 85±15 (approx. 26 March).There is some evidence for a complex seasonal inter-relationship between concentration and isotope ratio, both in the Cape Grim data and in Mook et al. (1983) South Pole data, but with marked differences between the stations, and with both different from the model estimates.In particular, the Cape Grim results suggest that exchange with Southern Hemisphere biosphere is the main contributor to the seasonal variation in isotope ratio at this latitude.     

An observational aircraft-based study of sea-breeze frontogenesis

In the summer of 1988/89 flights were carried out in the Coorong coastal area of South Australia to investigate sea-breeze fronts. The flights yielded data sets of the structure of the fronts in the cross-frontal direction with a spatial resolution of approximately 3 m. The study is focused on the budgets of sensible and latent heat in the vicinity of the front and on frontogenesis/frontolysis processes which are closely related to budget considerations.The frontogenesis relationships and the budgets were established on a 2 km length scale by low-pass filtering of the space series. As the wind components were measured with high accuracy, all processes which determine frontogenesis could be evaluated and are displayed in x,z-cross-sections: these are the confluence, shear and diabatic effects, all of which play a role in q/x-, q/z-, /x- as well as /z-frontogenesis. A detailed analysis is given for two different states of frontal development. The presented results shed much light on the governing physical processes in the frontal region with strong emphasis on the effects of confluence-generated updrafts, on shear instabilities causing bulges and clefts in the frontal surface as well as producing the elevated frontal head, and on processes related to differential heating and moistening.     

The Kolmogorov constant for carbon dioxide in the atmospheric surface layer over a paddy field

From measurements in the atmospheric surface layer over a paddy field, the Kolmogorov constants for CO₂ and longitudinal wind velocity were obtained. In this study, the nondimensional dissipation rate _nc = (1–16 _v )^-1/2 for CO₂ variance and = (1–16 _v )^-1/4 – _v for turbulent energy were used, assuming the equality of the local production term and the local dissipation term, and neglecting the divergence flux term in the budget equation. The value of the constant for CO₂ was consistent with recent determinations for temperature and humidity. The constant for longitudinal wind velocity showed good agreement with other recent observations.     

Estimates of diabatic wind speed profiles from near-surface weather observations

In this paper we analyse diabatic wind profiles observed at the 213 m meteorological tower at Cabauw, the Netherlands. It is shown that the wind speed profiles agree with the well-known similarity functions of the atmospheric surface layer, when we substitute an effective roughness length. For very unstable conditions, the agreement is good up to at least 200 m or z/L–7(z is height, L is Obukhov length scale). For stable conditions, the agreement is good up to z/L1. For stronger stability, a semi-empirical extension is given of the log-linear profile, which gives acceptable estimates up to ~ 100 m. A scheme is used for the derivation of the Obukhov length scale from single wind speed, total cloud cover and air temperature. With the latter scheme and the similarity functions, wind speed profiles can be estimated from near-surface weather data only. The results for wind speed depend on height and stability. Up to 80 m, the rms difference with observations is on average 1.1 m s^–1. At 200 m, 0.8 m s^–1 for very unstable conditions increasing to 2.1 m s^–1 for very stable conditions. The proposed methods simulate the diurnal variation of the 80 m wind speed very well. Also the simulated frequency distribution of the 80 m wind speed agrees well with the observed one. It is concluded that the proposed methods are applicable up to at least 100 m in generally level terrain.     

Bioaccumulation of Cobalt in Parmelia sulcata

Six locations across mainland Portugal were selected for exposing Parmelia sulcata, for a one-year period (8 months for one site), with simultaneous measurement of total (dry + wet) deposition (one-month periods). The exposed lichens and the total (dry + wet) deposition were analysed for cobalt contents by INAA (instrumental neutron activation analysis) and ICP-MS (inductively coupled plasma mass spectroscopy), respectively. The designated wet deposition was evaluated through the collected water volume; the designated dry deposition was assessed after the (dried) residual mass of the wet deposition. An excellent agreement between Co contents in exposed lichens and the cumulative (1) Co contents in the dry deposition, (2) dry deposition, and (3) wet deposition has been found for the locations with alternate drought and precipitation months, high dry deposition, and high Co contents in the latter. Continuous rainfall was found to hinder the Co accumulation in the lichen due to its release from the lichen and/or lower Co contents in the dry deposition. At three locations, P. sulcata Co contents, after subtraction of the background (before exposure), equalled or exceeded the Co contents in the cumulative dry deposition at the end of the exposure time. The optimal exposure period for this species likely depends on the exposure conditions.     

SODAR-based estimation of TKE and momentum flux profiles in the atmospheric boundary layer: Test of a parameterization model

Summary A simple parameterization for the estimation of turbulent kinetic energy (TKE) and momentum flux profiles under near-neutral stratification based on sodar measurements of the vertical velocity variance has been tested using data from the LINEX-2000 experiment. Measurements included operation of a phased-array Doppler sodar DSDPA.90 and of a sonic anemometer USA-1 mounted at a meteorological tower at a height of 90m. Good agreement has been found between the TKE and momentum flux values derived from the sonic and sodar data (with correlation coefficients r>0.90 and a slope of the regression lines of about 1.01.1) suggesting the possible use of sodar measurements of _w ² to derive turbulence parameter profiles above the tower range.     

The Influence of NaBr/NaCl Ratio on the Br--Catalysed Production of Halogenated Radicals

The activation of Br^- and Cl^- to atomic Br and Cl in sea-spray aerosol was investigated in smog-chamber experiments. In the presence of O₃, hydrocarbons and NaCl aerosol alone no activation was observed. By adding Br^- to the aerosol, the chain reaction: Br + O₃ BrO, BrO + HO₂ HOBr, HOBr HOBr(aq), HOBr(aq) + H⁺ + Br^- Br₂ (6), HOBr(aq) + H⁺ + Cl^- BrCl (7) was verified. The step from reaction (6) to (7) is accompanied by a decrease of the Br^-/Cl^- ratio from 1/600 to less than 1/2000. In the absence of sulphate, the chain is initiated by the reaction of OH(aq) with Br^-. The pH value decreases to less than 2 during the first minutes of the experiment and later on to almost 1 (in the absence of NO_x or SO₂). This is caused by the formation of oxalic acid from alkanes and toluene. In stopped flow experiments, the reduction of Br₂ by oxalic acid was observed to occur through a two-step mechanism: HC₂O₄ ^- + Br₂ Br^- + BrC₂O₄H (k₂₂, k_-22), BrC₂O₄H Br^- + H⁺ + 2 CO₂ (23) with the following rate constants and ratios of rate constants, k ± 2: k₂₂k_-23 / k_-22 = (2.9 ± 0.3) · 10^-4 s^-1, k_-22 / k_-23 = 7000 ± ₃₀₀₀ ¹³⁰⁰⁰ M^-1, k₂₂ = 2 ±_-1 ⁴ M^-1 s^-1, and k_-23 > 0.1 s^-1, k_-22 > 600 M^-1 s^-1. Oxalic acid may be responsible for the inhibition of the chain reaction observed at the end of the experiments.     

A new theory of the energy spectrum

In a recent paper, the author introduced a new viscous boundary layer, called the mesolayer, in turbulent shear flow. Its importance stems from its location between the inner and outer regions which are controlled by the law of the wall and Reynolds number similarity, respectively. This intrusion prevents the classical overlap assumption which appears to be fundamental in the derivation of the classical logarithmic behavior. The mesolayer has a thickness proportional to Taylor's microscale . This, and the analogy between the energy equation for the spectrum function of isotropic turbulence and the momentum equation for shear flow, suggest the existence of a similar region in wavenumber space with wavenumber k ~ ^-1. This mesoregion separates the inner region k ~ k _s(where k _s^-1 and is the Kolmogorov length) and the outer region k k _e(where k _e ^-1 and l is the energy-containing eddy size) and again invalidates the overlap assumption which appears to be fundamental in the derivation of the classical k ^-5/3-behavior of the inertial subrange.Incorporation of the mesoregion into the argument leads to a new theory with k ^-5/3-behavior in two regions (^-1 k k _s) and (k _e k ^-1) although with two different coefficients of proportionality (Kolmogorov constants). This leads to a wandering of the spectrum curve about the classical k ^-5/3 line similar to a wandering in turbulent shear flow about the logarithmic curve. This is clearly indicated by the data for the variation of the Kolmogorov constant.Other data support the new theory. In particular, the location of the point k _mwhere the curve of the nonlinear energy-transfer function goes through zero shows agreement with the theory, i.e., k _m^-1.     

The behaviour of aerosol optical depth during clear summer days in Athens,Greece

Summary The integral aerosol optical depths (k ) at the hour of 08:20 Local Standard Time (LST), are compared with those calculated previously at 11:20 and 14:20 LST, for clear days during summer in Athens over the period 1962–1988. The mean values at 08:20 LST were consistently lower than the values at 11:20 and 14:20 LST. The influence of the vertical wind profile on the values ofk was also investigated. A comparison was made of the wind profiles at 02:00 and 14:00 LST, for days in which the 11:20 and 14:20 LST values ofk were 0.200 andk 0.350, respectively. The corresponding bulk wind shear s was also found for the period 1980–1988. The most significant results occurred with the first category of days. The resultant wind velocities from the surface to the 900 hPa level, in each hour were higher by 2–4 m·s^–1 with respect to the corresponding values for the second category. At 02:00 LST the bulk wind shear showed a considerable difference (1.8) between the two categories of days in the surface to 700 hPa layer at 02:00 LST. Finally, the associated weather conditions that appear to initiate a period of low values ofk (k 0.200) at 11:20 and 14:20 LST were examined for the period 1980–1988. Fifteen such cases were identified and it was found that they all occurred after the passage of weak cold fronts.With 6 Figures     

Propagation of the sea-surface temperature anomalies in the Tropical Atlantic

Summary The evolving modes of the sea-surface temperature (SST) in the Tropical Atlantic on the short interannual (IA) timescale were obtained by performing the extended empirical orthogonal function (EEOF) analyses on this variable separately for the 106-year (1871–1976) and 20-year (1881–1900; 1901–1920; 1921–1940; 1941–1960) periods. The equatorial and inter-hemispheric patterns manifest in the first EEOF mode of each analysis as part of the short IA evolution of the SST anomalies in the Tropical Atlantic. Another outstanding feature of the first EEOF mode of each analysis concerns the propagations of the SST anomalies in the meridional direction within the 20°N–20°S band and in the zonal direction in the sector 40°W–20°W. For all analyses, the SST anomalies propagate northward from the equator to 15°N and southward from 20°N to 15°N, with the same sign anomalies merging approximately at 15°N. On the other hand, the SST anomalies propagate westward in the sector 40°W–20°W with a propagation rate close to that of the phase speed of the fastest baroclinic Rossby wave in the ocean. So, the observed propagations of the SST anomalies in the 20°N–20°S band might result from the combined effect of the surface oceanic currents in this band and the baroclinic Rossby waves in the ocean.     

On Trajectory Curvature as a Selection Criterion for Valid Lagrangian Stochastic Dispersion Models

Recently Wilson and Flesch (Boundary-Layer Meteorology, 84, 411-426, 1997) suggested that the average increment d z to the orientation = arctan(w/u) of the Lagrangian velocity-fluctuation vector can be used to distinguish the better Lagrangian stochastic models within the well-mixed class. Here it is demonstrated that the specification of d z constitutes neither a sufficient or universally applicable criterion to distinguish the better Lagrangian stochastic models within the well-mixed class. The hypothesis made by Wilson and Flesch that Lagrangian stochastic models with /P_E irrotational are zero-spin models, having d z=0, is proven     

On the turbulence structure in the stable boundary layer over the Greenland ice sheet

Turbulence measurements from a 30 m tower in the stably stratifiedboundary layer over the Greenland ice sheet are analyzed. The observationsinclude profile and eddy-correlation measurements at various levels. Atfirst, the analysis of the turbulence data from the lowest level (2 m aboveground) shows that the linear form of the non-dimensional wind profile(m) is in good agreement with the observations for z/L <0.4, whereL represents the Obukhov length. A linear regression yieldsm=1+5.8z/L. The non-dimensional temperature profile (h) at the2m level shows no tendency to increase with increasing stability. The datafrom the upper levels of the tower are analyzed in terms of both localscaling and surface-layer scaling. The m and the h values show atendency to level off at large stability (z/>0.4) where represents the local Obukhov length. Hence, the linear form of the functions is no longer appropriate under such conditions. The bestcorrespondence to the data can be achieved when using the expression ofBeljaars and Holtslag for m and h. The vertical profiles of theturbulent fluxes, the wind velocity variances and temperature variance arealso determined. The momentum flux profile and the profiles of wind speedvariances are in general agreement with other observations if a welldeveloped low-level wind maximum occurs, and the height of this maximum isused as a height scale.