Nitrate in the atmospheric boundary layer of the tropical South Pacific: Implications regarding sources and transport

Weekly bulk aerosol samples collected at Funafuti, Tuvalu (8°30S, 179°12E), American Samoa (14°15S, 170°35W), and Rarotonga (21°15S, 159°45W), from 1983 through most of 1987 have been analyzed for nitrate and other constituents. The mean nitrate concentration is about 0.11 g m^–3 at each of these stations: 0.107±0.011 g m^–3 at Funafuti; 0.116±0.008 at American Samoa; and 0.117±0.010 at Rarotonga. Previous measurements of mineral aerosol and trace metal concentrations at American Samoa are among the lowest ever recorded for the near-surface troposphere and indicate that this region is minimally affected by transport of soil material and pollutants from the continents. Consequently, the nitrate concentration of 0.11 g m^–3 can be regarded as the natural level for the remote marine boundary layer of the tropical South Pacific Ocean. In contrast, over the tropical North Pacific which is significantly impacted by the transport of material from Asia and North America, the mean nitrate concentrations are about three times higher, 0.29 and 0.36 g m^–3 at Midway and Oahu, respectively. The major sources of the nitrate over the tropical South Pacific are still very uncertain. A very significant correlation between the nitrate concentrations at American Samoa and the concentrations of ²¹⁰Pb suggests that transport from continental sources might be important. This continental source could be lightning, which occurs most frequently over the tropical continents. A near-zero correlation with ⁷Be indicates that the stratosphere and upper troposphere are probably not the major sources. A significant biogenic source would be consistent with the higher mean nitrate concentrations, 0.16 to 0.17 g m^–3, found over the equatorial Pacific at Fanning Island (3°55N, 159°20W) and Nauru (0°32S, 166°57E). The lack of correlation between nitrate and nss sulfate at American Samoa does not necessarily preclude an important role for marine biogenic sources.     

Solubilities of pyruvic acid and the lower (C1-C6) carboxylic acids. Experimental determination of equilibrium vapour pressures above pure aqueous and salt solutions

Henry's law constantsK _H (mol kg^–1 atm^–1) have been determined at 298.15 K for the following organic acids: formic acid (5.53±0.27×10³); acetic acid (5.50±0.29×10³); propionic acid (5.71±0.34×10³);n-butyric acid (4.73±0.18×10³); isobutyric acid (1.13±0.12×10³); isovaleric acid (1.20±0.11×10³) and neovaleric acid (0.353±0.04×10³). They have also been determined fromT=278.15 K toT=308.15 K forn-valeric acid (ln(K _H)=–14.3371+6582.96/T);n-caproic acid (ln(K _H)=–13.9424+6303.73/T) and pyruvic acid (ln(K _H)=–4.41706+5087.92/T). The influence of 9 salts on the solubility of pyruvic acid at 298.15 K has been measured. Pyruvic acid is soluble enough to partition strongly into aqueous atmospheric aerosols. Other acids require around 1 g of liquid water m^–3 (typical of clouds) to partition significantly into the aqueous phase. The degree of partitioning is sensitive to temperature. Considering solubility and dissociation (to formate) alone, the ratio of formic acid to acetic acid in liquid water in the atmosphere (at equilibrium with the gas phase acids) is expected to increase with rising pH, but show little variation with temperature.     

Initial findings of recent investigations of air-snow relationships in the summit region of the Greenland ice sheet

The concentrations of⁷Be,²¹⁰Pb and major ions have been measured in acrosol and snow samples collected near Summit, Greenland (72°20N, 38°45W) in the summers of 1989 and 1990. Comparison to previous results from free tropospheric sampling of the North American Arctic indicates that some acrosol-associated species are as much as 50% depleted in near surface air over the Greenland Ice Sheet. It is shown that local atmospheric processes, particularly isolation of air masses beneath a near surface inversion, can exert dominant influence on the chemistry of surface-level air. These findings illustrate the extreme caution that must be taken if the results of surface-based atmospheric sampling are to be used to examine the relationship between the chemistry of the atmosphere and snow falling from it.Depth profiles of⁷Be in the surface layers of the snowpack near Summit suggest that up to half of the annual accumulation of snow may occur in the two to three month late spring-early summer period. If this is generally true for the Summit region, previous regional studies of snow chemistry that assumed linear dependence of age on depth to convert depth profiles to time series will have to be reassesed. However, spatial heterogeneity of near surface snow chemistry, that is currently not well understood, makes interpretation of the⁷Be profiles tentative at present.     

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).     

The Reactivity of Biogenic Monoterpenes towards OH· and SO4-· Radicals in De-Oxygenated Acidic Solution

The reactivity of some selected biogenic monoterpenecompounds towards important aqueous phase free-radicaloxidants, namely OH· and SO₄ ^-·, have beeninvestigated using the complementary experimentaltechniques of pulse radiolysis and laser flashphotolysis ( = 248 nm). Rate constants forthe reactions of the OH· radical with cis-verbenol andmethacrolein have been determined to be (6.8 ± 0.5) ×10⁹ dm³ mol^-1 s^-1 and (8.0± 0.7) × 10⁹ dm³ mol^-1s^-1,respectively (T = 20 °C, pH 4.0, Ionic strength 0 mol dm^-3). Rate constants and activationenergies for the reactions of the SO₄ ^-·radical have been measured for the following compounds(T = 20 °C, pH 4.0, Ionic strength = 0.03 moldm^-3): -pinene (k = (3.1 ± 0.1) ×10⁹ dm³ mol^-1 s^-1;E _act. =(8.9 ± 1.3) kJ mol^-1), -terpineol(k = (4.1 ± 0.1) × 10⁹ dm³mol^-1s^-1; E _act. = (13.4 ± 0.6) kJmol^-1), cis-verbenol (k = (3.2 ± 0.2) ×10⁹ dm³ mol^-1 s^-1;E _act. =(10.0 ± 0.7) kJ mol^-1), verbenone (k = (1.6± 0.1) × 10⁹ dm³ mol^-1s^-1;E _act. = (6.1 ± 0.7) kJ mol^-1), myrtenal(k = (1.85 ± 0.1) × 10⁹ dm³mol^-1s^-1; E _act. = (7.5 ± 0.7) kJmol^-1)and methacrolein (k = (1.18 ± 0.1) × 10⁹dm³ mol^-1 s^-1). In most instances theabsorption spectra of the intermediate products formedby these reactions have been measured which, inconjunction with strategic conductiometric studies,have been used to suggest plausible mechanisms for theoxidation in acidic de-oxygenated solution.     

Tidal currents off the antarctic ice barrier,Queen Maud Land

Observations of tidal currents in lat. 71° 01 S, long. 10° 55 W indicate that a semi-diurnal tidal wave progresses towards the WSW, that is, parallel to the main direction of the barrier. ForM ₂ the cotidal hour appears to be about 7^h, in good agreement with the value 6.7^h, that is derived from observations of the atmospheric pressure. Furthermore, the current measurements indicate that the ratio(K ₁+O₁)/(M₂+S₂) is large, perhaps as large as 2.5.

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Zusammenfassung Beobachtungen der Gezeitenströmungen in 71° 01 S und 10° 55 W lassen erkennen, daß eine halbtägige Gezeitenwelle gegen WSW, also parallel zur Hauptrichtung der Eisbarriere, wandert. FürM ₂ scheint das Flutstundenintervall etwa 7 Stunden zu betragen und damit gut zu dem Wert von 6,7 Stunden zu stimmen, der aus Beobachtungen des Luftdrucks abgeleitet wird. Ferner lassen Strömungsmessungen erkennen, daß der Quotient(K ₁+O₁)/(M₂+S₂) mit etwa 2,5 groß ist.

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Résumé Des observations des courants de marée, faites à 71° 01 S et 10° 55 W, montrent qu'une vague de marée semi-diurne progresse en direction WSW, ce qui est parallèle à la direction principale de la limite de la banquise. PourM ₂ l'heure cotidale paraît être de 7^h environ, ce qui correspond assez bien avec la valeur de 6.7^h déduite des observations de la pression atmosphérique. En outre les mesures du courant indiquent que le quotient(K ₁+O₁)/(M₂+S₂) est assez grand et comporte environ 2.5.

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With 1 Figure.     

High resolution spectral features of a series of aromatic hydrocarbons and BrO: Potential interferences in atmospheric OH-measurements

Naphthalene (C₁₀H₈), several other hydrocarbons, mostly derivates of naphthalene, and bromine oxide (BrO) were analyzed for narrow band (0.01 nm) absorption lines in the wavelength range between 307.7 and 308.3 nm to study their potential impact on OH radical measurements by differential absorption spectroscopy.Only naphthalene showed narrow band absorption lines in this wavelength region. From nine naphthalene lines the differential absorption cross-section was determined.The strongest naphthalene line at 308.002 nm is close to the Q ₁(2) OH line, but about a factor of 200 weaker (=(65.2±15.3)×10^-20 cm²/molec). The corresponding detection limit for naphthalene is about 15 ppt. We re-evaluated some spectra of our OH measurement campaign in July 1987 with respect to naphthalene and obtained an upper limit of 30 ppt for its concentration.BrO was recorded in the larger wavelength interval between 307.7 and 308.7 nm. Structured absorptions were only observed at wavelengths above 308.2 nm and no significant structures were found in the vicinity of the Q ₁(2) and Q ₁(3) OH lines.     

Variations in atmospheric CO2 at the Meteorological Research Institute, Tsukuba, Japan

Since April 1986, measurements of the CO₂ concentration in the surface air have been conducted at the Meteorological Research Institure (MRI, 36°04 N, 140°07 E, 25 m above sea level) in Tsukuba, located 50 km northeast of Tokyo, Japan. The CO₂ data measured over times between 11:00 Japan Standard Time (JST) and 16:00 JST (C _N ) were considered to be representative of the air (within a few ppmv) in the planetary boundary layer. To evaluate the representative CO₂ level on a spatial scale larger than that of the C _N record, the CO₂ data with hour-to-hour variation less than 1 ppmv were selected (C _P ). Comparison of these data with those of Ryori (39°02 N, 141°50 E), a continental station operated by the Japan Meteorological Agency, indicates that the C _P record provides a representative CO₂ level in the air on spatial scales of at least a few hundred kilometers.The C _N record allows an investigation of the internanual changes in photosynthesis/respiration against changes in climatological parameters. Within a small temperature anomaly (ca.±1 °C) respiration is sensitive to the temperature change, while photosynthesis is less sensitive. When the temperature anomaly is large, however, photosynthesis and respiration tend to be competitive.     

Application of Lead Isotopic Ratios in Atmospheric Pollution Studies in the Valley of Mexico

Lead isotopic studies of airborne particulate matter, gasoline and other environmental samples have been carried out to determine possible sources of lead pollution in the Metropolitan Zone of the Valley of Mexico. ²⁰⁶Pb/²⁰⁷Pb ratio in gasoline was 1.1395 ± 0.0165 and 1.071 ± 0.008 for industrially-derived lead as a mean. Natural lead is more radiogenic with values from 1.2082 ± 0.022 to 1.211 ± 0.108. The measured Pb isotopic signature of airborne particulate matter reflects the relative importance of each of these sources. The ²⁰⁶Pb/²⁰⁷Pb ratio was 1.179 ± 0.105 as a mean. The relative importance of gasoline has decreased, and, therefore, other sources (natural and industrial) can be identified by means of isotopic studies. This is a consequence of the introduction of unleaded gasoline as mandaped by strictest environmental regulation.     

Factors Influencing the Atmospheric Depositional Fluxes of Stable Pb, 210Pb, and 7Be into Chesapeake Bay

Atmospheric depositional fluxes of ⁷Be and²¹⁰Pb (bulk) and stable Pb (wet) were measuredsimultaneously for one year (from September 1995–August 1996) atStillpond, Maryland on the uppereastern shore of the Chesapeake Bay. The annual total(bulk) depositional fluxes of ²¹⁰Pb and ⁷Bewere 0.78 and 13 dpm cm^-2, respectively, andagree well with other previously reported results atnearby locations such as Norfolk, VA and Lewes, DE. The wet depositional flux of stable Pb (58 ng cm^-2 yr^-1)was also similar to thatmeasured at other Chesapeake sites during 1990–1991(55 ng cm^-2 yr^-1, for both Wye and Elms,Maryland). This suggests that a constant Pb flux hasbeen reached since the mandatory use of unleadedgasoline was instituted. The concentrations of⁷Be, ²¹⁰Pb, and to a lesser extent stable Pbwere diluted exponentially by precipitation, based onconcentrations versus precipitation plots. Due tohigher enrichment of ²¹⁰Pb in the lowertroposphere, the dilution effect was largest on²¹⁰Pb (i.e., controlled mainly by below-cloudscavenging processes), and thus its depositional fluxincrease is negligible as precipitation amountincreases. A good correlation between the amount ofprecipitation and total depositional flux of ⁷Beand stable Pb, which are more enriched in the uppertroposphere, suggests that precipitation amount isimportant in controlling their fluxes (i.e.,controlled by both below-cloud scavenging and in-cloudcondensation processes). Based on ⁷Be versus²¹⁰Pb plots, it appears that ⁷Be, relativeto ²¹⁰Pb, is less efficiently scavenged bysnowfall. Our results suggest that in addition toprecipitation amounts, marine air-mass transport orsnowfall may be important factors in controlling theseasonal variability of the fallout fluxes of tracemetals in coastal areas.     

Annual variation of atmospheric carbonyl sulfide in the marine atmosphere in the Southern Indian Ocean

Measurements of the concentrations of carbonyl sulfide (COS) in the marine atmosphere were made over a period of two years in the southern Indian Ocean (Amsterdam Island, 37°50 S–77°31 E; March 1987–February 1988 and April 1989–February 1990). The mean atmospheric COS concentration for the whole period was 475±48 pptv (n=544). Atmospheric COS concentrations show no significant seasonal variation with a summer to winter ratio of 1.05. Taking into account the observed variability of the atmospheric COS concentration (10%), a value of 1.4 yr is estimated as a lower limit for the atmospheric COS lifetime. A comparison of the COS data at Amsterdam Island with those obtained in the Southern Hemisphere in the past 12 yr does not reveal any significant trend in the tropospheric background COS mixing ratio.     

Seasonal variations of atmospheric sulfur dioxide and dimethylsulfide concentrations at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric sulfur dioxide (SO₂) concentrations were performed from March 1989 to January 1991 at Amsterdam Island (37°50 S–77°30 E), a remote site located in the southern Indian Ocean. Long-range transport of continental air masses was studied using Radon (²²²Rn) as continental tracer. Average monthly SO₂ concentrations range from less than 0.2 to 3.9 nmol m^-3 (annual average = 0.7 nmol m^-3) and present a seasonal cycle with a minimum in winter and a maximum in summer, similar to that described for atmospheric DMS concentrations measured during the same period. Clear diel correlation between atmospheric DMS and SO₂ concentrations is also observed during summer. A photochemical box model using measured atmospheric DMS concentrations as input data reproduces the seasonal variations in the measured atmospheric SO₂ concentrations within ±30%. Comparing between computed and measured SO₂ concentrations allowed us to estimate a yield of SO₂ from DMS oxidation of about 70%.     

A smog chamber for studies of the reactions of terpenes and alkanes with ozone and OH

The design and performance of a smog chamber for the study of photochemical reactions under simulated environmental conditions is described. The chamber is thermostated for aerosol experiments, and it comprises a gas chromatographic sample enrichment system suitable for monitoring hydrocarbons at the ppbv level. By irradiating NO _x /alkane-mixtures rate constants for the reaction of OH radicals with n-alkanes are determined from n-pentane to n-hexadecane to be (k±2)/10^–12 cm³ s^–1=4.29±0.16, 6.2±0.6, 7.52 (reference value), 8.8±0.3, 10.2±0.3, 11.7±0.4, 13.7±0.3, 15.1±0.5, 17.5±0.6, 19.3±0.7, 22.3±1.0, and 25.0±1.3, respectively at 312 K. Rate constants, (k±2)/10^–17 cm³ s^–1, for the reaction of ozone with trans-2-butene (21.2±1.0), cis-3-methylpentene-(2) (47.2±1.7), cyclopentene (62.4±3.5), cyclohexene (7.8±0.5), cycloheptene (28.3±1.5), -pinene (8.6±1.3), and -pinene (1.4±0.2) are determined in the dark at 297 K using cis-2-butene (13.0) as reference standard.     

Calculation of velocity skewness in real and artificial plant canopies

Wind velocities within a plant canopy are much more strongly skewed than those of the air flow above. We have examined the governing Eulerian equations for the velocity products u _i, u _j u_k using data from a wind tunnel study with an artificial canopy consisting of an array of 5 cm lengths of monofilament fishing line, and from measurements in corn (Zea mays L).Simple parameterizations for pressure-velocity correlations, and for the quadruple velocity products allowed reasonably accurate calculations of the third moments using measured profiles of the mean velocity, variance and covariance fields. Comparisons of individual terms in the rate equations for ovu _i, u _j u _krevealed that diffusion (from above) and mean shear were most important in creating large skewness in the canopy. A drag term also contributed but was of lesser importance. These terms were balanced by return-to-isotropy and a turbulence interaction term. A quasi-Gaussian approximation considerably underestimated the magnitude of the fourth moments within the canopy.     

Nitrogen and sulfur species in Antarctic aerosols at Mawson,Palmer Station,and Marsh (King George Island)

High volume bulk aerosol samples were collected continuously at three Antarctic sites: Mawson (67.60° S, 62.50° E) from 20 February 1987 to 6 January 1992; Palmer Station (64.77° S, 64.06° W) from 3 April 1990 to 15 June 1991; and Marsh (62.18° S, 58.30° W) from 28 March 1990, to 1 May 1991. All samples were analyzed for Na⁺, SO ₄ ^2– , NO ₃ ^– , methanesulfonate (MSA), NH ₄ ⁺ ,²¹⁰Pb, and⁷Be. At Mawson for which we have a multiple year data set, the annual mean concentration of each species sometimes vary significantly from one year to the next: Na⁺, 68–151 ng m^–3; NO ₃ ^– , 25–30 ng m^–3; nss SO ₄ ^2– , 81–97 ng m^–3; MSA, 19–28 ng m^–3; NH ₄ ⁺ , 16–21 ng m^–3;²¹⁰Pb, 0.75–0.86 fCi m^–3. Results from multiple variable regression of non-sea-salt (nss) SO ₄ ^2– with MSA and NO ₃ ^– as the independent variables indicates that, at Mawson, the nss SO ₄ ^2– /MSA ratio resulting from the oxidation of dimethylsulfide (DMS) is 2.80±0.13, about 13% lower than our earlier estimate (3.22) that was based on 2.5 years of data. A similar analysis indicates that the ratio at Palmer is about 40% lower, 1.71±0.10, and more comparable to previous results over the southern oceans. These results when combined with previously published data suggest that the differences in the ratio may reflect a more rapid loss of MSA relative to nss SO ₄ ^2– during transport over Antarctica from the oceanic source region. The mean²¹⁰Pb concentrations at Palmer and Marsh and the mean NO ₃ ^– concentration at Palmer are about a factor of two lower than those at Mawson. The²¹⁰Pb distributions are consistent with a²¹⁰Pb minimum in the marine boundary layer in the region of 40°–60° S. These features and the similar seasonalities of NO ₃ ^– and²¹⁰Pb at Mawson support the conclusion that the primary source regions for NO ₃ ^– are continental. In contrast, the mean concentrations of MSA, nss SO ₄ ^2– , and NH ₄ ⁺ at Palmer are all higher than those at Mawson: MSA by a factor of 2; nss SO ₄ ^2– by 10%; and NH ₄ ⁺ by more than 50%. However, the factor differences exhibit substantial seasonal variability; the largest differences generally occur during the austral summer when the concentrations of most of the species are highest. NH ₄ ⁺ /(nss SO ₄ ^2– +MSA) equivalent ratios indicate that NH₃ neutralizes about 60% of the sulfur acids during December at both Mawson and Palmer, but only about 30% at Mawson during February and March.     

Free convection scaling over the ocean derived from buoy measurements during gate

The structure of atmospheric turbulence in the surface layer over the open ocean is examined under conditions of local free convection. The raw data consist of profile and fluctuation measurements of wind and temperature as obtained from a meteorological buoy. For near neutral conditions and for waves running approximately along the wind direction, wave-induced wind fluctuations can be described by a simplified linear theory based on Miles (1957). In this case, the spectrum of wind velocity is given as the sum of two parts; for the turbulent part, the parameterization as obtained by Kaimal et al. (1972) applies, while the wave-induced part is parameterized using a simplification of Miles' linear theory. For cases of local free convection, the measurements of the vertical component of the wind velocity are well described by similarity theory; as expected, _w /(-uw)^1/2 is proportional to (- z/L)^1/3. In order to scale the longitudinal wind velocity component, it seems to be reasonable to extend the list of relevant parameters by the height of the mixed layer z _i. We obtain _u /(- uw)^1/2 (z/z _i)^1/3(- z/L)^1/3 with only a poor correlation coefficient of r = 0.6. Overall, the results of local free convection scaling obtained from direct measurements show good agreement with those obtained from profile measurements. A comparison between direct and indirect determination of turbulent fluxes of momentum shows an unexplained difference of about 20%. This discrepancy is mainly due to a gap in the uw-cospectrum at the swell frequency.     

Energy flux partitioning over the Amazon forest

The present study involved determination of the experimental energy receipt partitioning over the tropical Amazon forest. Diurnal variation of net radiation (Q ^*), sensible heat flux (Q _H) and latent heat flux (Q _E) is presented. The daytimeQ _E is in phase withQ ^* and it is always an important term in the energy balance. The daily averagedQ _E is 59 to 100% of the dailyQ ^* whereasQ _H is 5 to 28% at the Amazon forest site (2° 57 S; 59° 57 W) for the sample periods. The results present evidence thatQ _E over the Amazon forest is greater thanQ ^* in the afternoon hours. The role of sensible heat advection in maintaining largeQ _E over the forest surface is discussed. Hourly Bowen ratio () values for two campaigns of the Amazon forest micrometeorological experiment are presented. During daylight hours, the differences in are not significant, and exhibit a systematic pattern. The only time that the variation in Bowen ratio increased significantly was at sunrise and sunset when the thermal structure of the air was changing from a strong inversion to lapse and vice versa. The diurnal values changed from –3.50 to 0.85. The mean hourly calculated from values from 07.00 to 16.00 h, varied from 0.05 to 0.85.Diese Studie beschäftigt sich mit der Aufteilung der empfangenen Energie über dem tropischen Amazonasurwald. Es wird der Tagesgang der Strahlungsbilanz (Q ^*), des fühlbaren (Q _H) und des latenten Wärmestromes (Q _E) vorgestellt. Während der Tagesstunden istQ _E in Phase mitQ ^* und ist immer ein wichtiger Term der Energiebilanz. Das Tagesmittel vonQ _E beträgt 59 bis 100%,Q _H 5 bis 28% des täglichenQ ^* an den Meßtagen bei der Amazonasurwaldstation (2° 57 S; 59° 57 W). Die Ergebnisse legen nahe, daß in den NachmittagsstundenQ _E über dem Amazonasurwald größer ist alsQ ^*. Die Rolle der Advektion von fühlbarer Wärme zur Aufrechterhaltung des großenQ _E über der Waldoberfläche wird diskutiert. Für zwei Meßkampagnen wurden die stündlichen Bowenverhältnisse () vorgestellt. Während der Tagesstunden ergaben sich keine signifikanten Änderungen von, während bei Sonnenaufgang und -untergang, wenn der thermische Aufbau der Luft von einer starken Inversion zu neutral und umgekehrt wechselt, die Unterschiede deutlich anstiegen. Die Tageswerte von lagen zwischen –3.50 und 0.85. Die Stundenmittel von 7.00 bis 16.00 Uhr schwankten zwischen 0.05 und 0.85.

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With 3 Figures     

Zur Frage des Ersatzes psychrometrischer Tafeln durch Rechenschieber

Zusammenfassung Nach der zur Berechnung der relativen Feuchtigkeit aus Psychrometerablesungen aufgestellten Sprungschen Formel sind graphische Tafeln in verschiedenen Ausführungen hergestellt worden. Um das Ableseverfahren zu vereinfachen, ist auch versucht worden, diese zweidimensionalen Darstellungen durch einen einfachen Rechenschieber zu ersetzen; doch müßte in diesem Fall die Psychrometerformel die Bedingung erfüllenR=100 f(t)/f(t) (t=Trockentemperatur,t=Feuchttemperatur), was die Sprungsche Formel nicht tut. Es läßt sich nun eine andere Formel aufstellen, mit deren Hilfe man schon mit einer mäßigen Annäherung auskommt, wenn man die Skaleneinteilung fürR (bzw. logR) etwas korrigiert und Abweichungen bis zu 2 1/2% in Kauf nimmt.

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Summary According to Sprung's formula for obtaining the relative humidity from psychrometer-readings, graphs have been produced. For simplifying the method of reading it has been tried to replace the two-dimensional arrangement by a simple slide rule; in this case the psychrometric formula should correspond to the equationR=100 f(t)/f(t) (t=dry temperature,t=wet bulb temperature), which is not fulfilled by Sprung's formula. Another formula is therefore here developed, leading to a satisfactory approximation, provided that the division of theR-scale be somewhat modified and differences be allowed up to 2 1/2%.

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Résumé Pour déduire l'humidité relative des observations psychrométriques on emploie généralement la formule de Sprung ou des tableaux graphiques en diverses formes reposant sur celle-ci. Pour simplifier la procédure de lecture on a aussi essayé de remplacer ces représentations bi-dimensionelles par un simple curseur. Dans ce cas la formule psychrométrique devrait remplir la conditionR=100 f(t)/f(t) (t=température sèche,t=température mouillée), ce qui ne correspond pas à la formule de Sprung. Pour cette raison, on a développé une autre formule qui permet une approximation suffisante à condition que l'on corrige légèrement l'échelle pourR et qu'on admet des écartes jusqu'a 2 1/2%.

     

Recurrence statistics of concentration fluctuations in plumes within a near-neutral atmospheric surface layer

This study examines the statistical properties of the concentration derivative, , for a dispersing plume in a near-neutrally stratified atmospheric surface layer. Towards this goal, the probability density function (pdf) of , and the conditional pdf of given a fixed concentration level, , have been measured. These pdfs are found to be modeled well by a generalizedq-Gaussian (gqG) distribution with intermittency exponent,q, equal to 0.3 and 3/4, respectively. These results highlight the strong intermittency effect (patchiness) of the small-scale concentration eddy structures in the plume. The distribution of time intervals between successive high peaks in the squared derivative process, x², is found to be well approximated by a power-law distribution, implying that occurrences of these high peaks are much more clustered than would be predicted by a Poisson or shot-noise process. The results are used to improve models for the joint pdf of and , and for the expected number of upcrossings per unit time interval of a fixed concentration level that have been proposed by Kristensenet al. (1989). The predictions of the improved models are in accord with observations, and suggest that the intercorrelation between and must be explicitly incorporated if good estimates of the upcrossing intensity are to be obtained.     

Kinetics of the reactions of hydroxyl radicals with aliphatic ethers studied under simulated atmospheric conditions: Temperature dependences of the rate coefficients

Rate coefficients have been measured for the reactions of hydroxyl radicals with five aliphatic ethers over the temperature range 242–328 K. Competitive studies were carried out in an atmospheric flow reactor in which the hydroxyl radicals were generated by the photolysis of methyl nitrite in the presence of air containing nitric oxide. The reaction of OH with 2,3-dimethyl-butane was used as the reference reaction and the following Arrhenius parameters have been obtained for the reactions: OH+RORproducts: