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.     

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).     

Studies of the atmospheric stability characteristics during the solar eclipse of February 16, 1980

Observations made with a monostatic sodar and from a 120 m instrumented tower have been used to study the variations in the atmospheric boundary layer at Tarapur (19° 50 N, 72° 41 E) during the solar eclipse of February 16, 1980. Atmospheric instability was reduced below normal values during the eclipse but the atmosphere at no time became stable.     

High-Latitude Springtime Photochemistry. Part I: NOx, PAN and Ozone Relationships

Springtime measurements of NO_x, ozone, PAN,J(NO₂), and other compounds were made near Ny-Ålesund,Svalbard (78°54N, 11°53E), in 1994 and Poker Flat,Alaska (65°08N, 147°29W), in 1995. At Svalbard medianmixing ratios for PAN and NO_x of 237 and 23.7 pptv,respectively, were observed. The median mixing ratios at Poker Flat for PANand NO_x were 79.5 and 85.9 pptv, respectively. These data areused to estimate thermal PAN decomposition using several differentapproaches. At Svalbard PAN decomposition was very small, while at PokerFlat up to 30 pptv/h PAN decomposed. At both sites the NO_x/PANratio increased with temperature between –10 and 20°C implyingthat PAN decomposition is an important NO_x source. In-situozone production was calculated from the measured NO, NO₂,O₃, J(NO₂), and temperature data, using thesteady state assumption Median ozone production was 605 pptv/h at PokerFlat, and one order of magnitude smaller at Svalbard during the daytime.Only at Poker Flat could a direct influence on the diurnal ozone cycle beobserved from in-situ production. These results imply that PAN decompositionis a major source of NO_x in the high latitude troposphere, andthat this contributes to the observed spring maximum in surface ozone.     

Wind characteristics in the lowest 340 m of the atmospheric boundary layer at Pune,India

Wind characteristics in the lowest 340 m (agl) of the atmospheric boundary layer at Pune (18°32N, 73°51E, 559 m ASL) have been investigated using the pilot balloon wind observations obtained during the summer monsoon seasons of 1976, 1979 and 1980. Variations in the zonal and meridional components of wind at the surface, 40, 150 and 340 m (agl) have been described. Frequency distribution of the zonal component showed an unimodal character at the surface, which gradually approached a multimodal character at 340 m. The distribution pattern of the wind components was, by and large, normal. Spectral analysis of the wind components showed that the spectral energy was predominantly shared by 5–7 and 2–3 day periods.     

The application of a two-dimensional numerical model of the planetary boundary layer to the Nanticoke region on the north shore of Lake Erie

A two-dimensional atmospheric boundary-layer model is applied to the Nanticoke region on the northern shore of Lake Erie (80 ° 03W and 42 ° 50N) to simulate numerically the observed wind and temperature profiles. In general, the profiles predicted by the model agree reasonably well with the observed profiles.     

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.     

Diurnal variation of horizontal wind direction fluctuations in complex terrain at Geysers,Cal.

Horizontal diffusion in the surface layer is dependent on the standard deviation of wind direction fluctuations . Diurnal variation of this parameter in complex terrain was studied for the July 1979 Geysers, Cal., experiment using data from a network of 11 short meteorological towers in the 25 km² Anderson Creek watershed Valley side slopes are roughly 20 ° and maximum terrain difference is about 1 km.Values of for wind directions sampled for one hour at a height of 10 m are about 35 ° during the daytime. They slowly decrease to about 20 ° by 8 to 10 p.m. as stability increases but wind speeds are still relatively high. After 10 p.m. the drainage flow sets in at most stations, with speeds of 1 to 2 m s^-1, and average increases to about 30° during the period 11 p.m. to 6 a.m. In general, highest values of at night are associated with lowest values of wind speed and greatest static stability. This enhancement of by the terrain suggests that horizontal diffusion at night always conforms to that expected during nearly neutral stabilities. That is, Pasquill class D diffusion applies to the horizontal component all night in complex terrain.     

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.     

Sea breeze activity at an inland station Kharagpur (India) — A case study

Surfaces fluxes, turbulent kinetic energy and Flux Richardson number are calculated for three typical sea breeze days characterizing three types of sea breeze onset at an inland station Kharagpur (22°21 N, 87°19 E), 80 km inland, one of the sites for MONTBLEX (MONsoon Trough Boundary Layer EXperiment), in India. The sea breeze onset is associated with a decrease in momentum and heat fluxes and an increase in moisture flux. The turbulent kinetic energy shows quite a significant value even in the late afternoon. The surface layer becomes nearly stable even before sunset, due to the passage of the sea breeze.     

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.     

Study of the influence of katabatic flows on the Antarctic circulation using GCM simulations

Summary A one dimensional analytical model of katabatic wind over the Antarctica has been developed. This parametric model is derived from the bulk two-layer model of Ball including the surface friction and taking into account the Earth's rotation and the geostrophic wind in the upper layer.This model is validated using the data set (70 soundings) collected during IAGO experiment at D47 (67°24S, 138°43E, altitude 1 564m), 110 km inland from the coast of Adélie Land.The parameteric model is then introduced into a GCM which is a spectral global version of the operational numerical weather prediction model used by the French weather service. The most significant effect of the parameterization is a 50 m increase of the geopotential height over the South Pole. The surface temperature at the South Pole increases (2°C) reducing the pole-midlatitude thermal gradient. The westerly circulation at 50° S is slowed down (4m/s at 850 hPa), and the surface pressure at the South Pole increases (4hPa). These results, consistent with an increase of katabatic winds, would however be improved by a better coupling between the parameterization and the GCM boundary layer.With 8 Figures     

Glaciers and Climate in the Andes between the Equator and 30° S: What is Recorded under Extreme Environmental Conditions?

Sublimation and melt disturb the environmental information obtained from ice core records in the Andes. In two case studies we demonstrate to what extent these post-depositional processes may remove major parts of the accumulated snow cover. Dark ash layers from the Tungurahua eruption changed the albedo of surface snow on Chimborazo glacier (6268 m, 1°30 S,78°36 W, Ecuador) between two ice core drilling campaigns and forced substantial melt. Re-distribution and washout of the chemical constituents shifted the concentration profiles obtained in December 1999 as compared to an equivalent core drilled in December 2000. The stable isotope records showed that approximately the water equivalent (weq) of an annual layer had melted, and that the percolating melt water penetrated within the firn layer to a depth of at least 16.5 m without refreezing. In the second example, from a site on the dry axis between the tropical and extra-tropical precipitation belts, significant loss of accumulated snow layers occurred by sublimation. A surface experiment at Cerro Tapado glacier (5536 m, 30°08 S,69°55 W, Chile) revealed that losses of 2 mm weq (5 mm snow) per day occurred during the dry period following the 1997/98 El Niño. This loss generally included the entire surface layer enriched in stable isotopes, and thus caused minimal disturbance of the isotopic signature (and hence climatic information) of the net accumulation, yet chemical constituents again experienced considerable changes in concentration. From annual layer counting and direct dating it is obvious that the major part of the accumulated ice on both glaciers is younger than 100 years; however, isotopic and chemical variations at least in the basal ice from Cerro Tapado clearly point to climate conditions different from the recent centuries. This evidence is supported by mass balance considerations derived from a glacier-climate model. The possibility of a third type of disturbance aside from sublimation and melting – in this case a significant hiatus in the environmental chronology – also deserves consideration for other icecore records from this region. Potential disruptions or discontinuities need to be carefully evaluated given the profound changes in climatic and glaciological conditions since the Last Glacial Maximum throughout Holocene times.     

Cold surges along the front range of the Rocky mountains: Development of a classification scheme

Summary A classification scheme for cold surges occurring along the Front Range of the Rocky Mountains has been developed using NMC surface and upper air data. A separation is seen in the data between cases with parent anticyclones that moved from Canada south into the United States (Northern type) and those which moved from the Eastern Pacific Ocean east into the central US (Western type). The Northern surges are further broken down into three types, A, B and B, when the degree of southward motion of the anticyclone and the leading edge of the cold air is considered. An anticyclone movement south of 40°N distinguishes type A, while anticyclone tracks remaining north of 40°N characterize types B and B. The leading edge of the surge (the surge line) associated with the type A anticyclone travels south of 25N, while the type B anticyclones produce two distinct surge line movements, one remaining north of 25°N and the other moving south of 25°N. It is not possible to break down the Western surges into distinct types. As a rule, the anticyclones associated with Western surges remain between 50°N and 30°N, with the surge line moving south to 18°N on average.Though the classification scheme is developed in a relatively subjective manner, the statistical robustness of the scheme is verified through application of the nonparametric Mann-Whitney test. Results of the test clearly provide support for the division of the surges that was obtained.With 16 Figures     

Seasonal variation of atmospheric dimethylsulfide at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric concentrations of dimethylsulfide (DMS) were carried out for two years in a marine site at remote area: the Amsterdam Island (37°50S–77°31E) located in the southern Indian Ocean. DMS concentrations were also measured in seawater. A seasonal variation is observed for both DMS in the atmosphere and in the sea-surface. The monthly averages of DMS concentrations in the surface coastal seawater and in the atmosphere ranged, respectively, from 0.3 to 2.0 nmol l^-1 and from 1.4 to 11.3 nmol m^-3 (34 to 274 pptv), with the highest values in summer. The monthly variation of sea-to-air flux of DMS from the southern Indian Ocean ranges from 0.7 to 4.4 mol m^-2 d^-1. A factor of 2.3 is observed between summer and winter with mean DMS fluxes of 3.0 and 1.3 mol m^-2 d^-1, respectively.     

Climatology of Ozone, PAN, CO, and NMHC in the Free Troposphere Over the Southern North Atlantic

Free tropospheric measurements of ozone, peroxyacetylnitrate andprecursors (CO, NMHC) that were made within the framework of the EUROTRACsub-project TOR (Tropospheric Ozone Research) between 1990 and 1995 at theGAW station Izana, Tenerife (28°18N, 16°30W) arediscussed. The average annual cycles reveal the importance of transport fromnorthern mid-latitudes and the role of photo-chemistry. According toair-mass trajectories, which were supplied to us from AEROCE(Atmosphere/Ocean Chemistry Experiment), transport from northernmid-latitudes is associated with high precursor concentrations in winter,whereas ozone concentrations in winter are not much influenced by transportpatterns, suggesting a rather uniform distribution over the northern part ofthe Northern Hemisphere around mean value of 43 ± 5 ppb. In summer,high ozone concentrations of up to 90 ppb are often encountered duringtransport from north, while the levels of precursors are much lower than inwinter, because of photochemical destruction. Trajectories from southerlylatitudes and the Sahara usually have the lowest ozone concentrationsassociated with them.     

Holocene Climate and the Development of a Subarctic Peatland near Inuvik, Northwest Territories, Canada

Multi-proxy paleoecological analyses were carried out on cores from a peatland in the continuous permafrost zone, to determine the effect of past climatic change on peatland development. Stratigraphy, bulk density and organic matter content were analyzed for eight cores from Campbell Creek peatland (69°17.3N, 133°15W). Detailed pollen and macrofossil analyses were carried out on two cores, and stable isotope analysis on one of those cores. The results indicate a succession, starting at 9000-9500 BP, from an open water mineral wetland with aquatic plants, to a fen dominated by Drepanocladus mosses and sedges, and then a change to a Sphagnum-dominated ombrotrophic vegetation typical of most of the peatland today. The beginning of the latter transition appears to coincide with the end of the early Holocene warm period. The physical stratigraphies of the other six cores indicate that a similar successional sequence occurred across the peatland, with some local variation. The transition to ombrotrophic conditions may be associated with the aggradation of permafrost in the peatland, in response to regional cooling. The effect of climate cooling on the peatland was probably indirect, through the aggradation of permafrost and associated hydrological changes.     

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.     

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.     

Clear sky ultraviolet-B radiation in the English Midlands: A comparison of measured and modelled values

Summary Spectral measurements were made of solar ultraviolet-B (UVB) irradiance at Sutton Bonington (52° 50N, 1° 15W) under cloudless skies using a Licor LI 1800 scanning spectroradiometer. The finite bandpass of the instrument and the steep shape of the UVB spectra caused overestimation of irradiance at short wavelengths. Spectra were corrected mathematically for these effects.The corrected spectra were compared to estimates of global UVB irradiance as a function of zenith angle and amount of ozone. Comparisons were made at 300 nm, 310 nm and 320 nm. Estimates were significantly greater (p = 0.05) than the measurements except at 320 nm where differences were not significant. The differences may have been the result of overestimation of UVB at short wavelengths, since some of the assumptions on which the estimates were based may not be valid for Sutton Bonington conditions.

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Zusammenfassung Unter wolkenlosem Himmel wurden in Sutton Bonington (52° 50N, 1° 15W) mittels eines Licor LI 1800 Spektroradiometer-Scanners Spektralmessungen von Ultraviolett-B (UVB)-Strahlung durchgeführt. Die endliche Bandbreite des Instruments und der steile Anstieg der UVB-Spektren führten zu einer Überschätzung der Strahlung im kurzwelligen Bereich. Die Spektren wurden in dieser Hinsicht mathematisch korrigiert.Die korrigierten Spektren wurden mit den Schätzwerten der globalen UVB-Strahlung — als Funktion von Zenithwinkel und Ozonmenge — bei 300nm, 310nm und 320nm verglichen. Hiebei erwiesen sich die Schätzwerte wesentlich höher (p = 0,05) als die Meßwerte, nur bei 320nm waren die Unterschiede nicht signifikant. Die Unterschiede könnten aus der Überschätzung von UVB im kurzwelligen Bereich resultieren, da einige der Schätzungsvoraussetzungen auf die Bedingungen in Sutton Bonington nicht zutreffen dürften.

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On leave from Department of Agronomy and Soils, Washington State University, Pullman, WA, U.S.A.

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With 4 Figures