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At least 163 records · Page 9

The abundances of CH4, CH3D, NH3, and PH3 in the troposphere of Jupiter derived from high-resolution 1100-1200/cm spectra

High-resolution spectra of the 1100-1200/cm region of the central part of Jupiter obtained in March 1980 and April 1981 are analyzed. The best fit NH3 distribution curve reveals a higher than solar mixing ratio, the abundance of NH3 to that of H2 being (3.3 + or - 1.7) x 10 to the -4th, below the 147 K layer (greater than 0.6 atmosphere). If NH3 ice particles are introduced as an opacity source, the NH3 mixing ratio below the 147 K layer can be lowered, but the fit is worse than that given by the model that excludes NH3 ice particles. The best fit PH3 distribution curve exhibits a PH3/H2 mixing ratio of (8.3 + or - 2.0) x 10 to the -7th in the troposphere. In addition, a CH4/H2 mixing ratio of (2.5 + or - 0.4) x 10 to the -3rd is found in the troposphere.

Knacke, R. F.↗

Measurements of condensation nuclei in the Airborne Arctic Stratospheric Expedition - Observations of particle production in the polar vortex

The ER-2 Condensation Nucleus Counter (ER-2 CNC) was operated in the Airborne Arctic Stratospheric Expedition (AASE) in January and February 1989. The ER-2 CNC measures the mixing ratio of particles, CN, with diameters from approximately 0.02 to approximately 1 micron. The spatial distribution of CN in the Arctic polar vortex was found to resemble that measured in the Antarctic in the Spring of 1987. The vertical profile of CN in the vortex was lowered by subsidence. At altitudes above the minimum in the CN mixing ratio profile, CN mixing ratios correlated negatively with that of N2O, demonstrating new particle production. CN serve as nuclei in the formation of Polar Stratospheric Clouds (PSCs) and the concentration of CN can affect PSC properties.

Wilson, J. C.↗

Brominated organic species in the arctic atmosphere

Measurements are reported of four gas-phase, brominated organic species found in the Arctic atmosphere during March and April 1983. Volume mixing ratios for CH3Br, CH2BrCH2Br, CHBr3, and CH2Br2 were determined by gas chromatography/mass spectrometry analysis from samples taken Arctic wide, including at the geographic North Pole and during a tropopause folding event over Baffin Bay near Thule, Greenland. Methyl bromide mixing ratios were reasonably constant at 11 plus or minus 4 pptv, while the other three brominated organics showed a high degree of variability. Bromoform (2 to 46 pptv) was found to be the dominant contributor to gaseous organic bromine to the Arctic troposphere at 38 plus or minus 10 percent followed by CH2Br2 (3 to 60 pptv) at 29 plus or minus 6 percent. Both CH3Br and CH2BrCH2Br (1 to 37 pptv) reservoirs contained less than 20 percent of the organically bound bromine. Stratospheric samples, taken during a tropopause folding event, showed mixing ratios for all four species at levels high enough to support a stratospheric total volume mixing ratio of 249 pptv Br (888 ngBr/SCM).

Berg, W. W.↗

Airborne flux measurements of ammonia over the Southern Great Plains using chemical ionization mass spectrometry

Ammonia (NH 3 ) is an abundant trace gas in the atmosphere and an important player in atmospheric chemistry, aerosol formation and the atmosphere-surface exchange of nitrogen. It is recognized as a major source of aerosol pollution, and it may limit the formation of cloud nuclei in remote or cold parts of the atmosphere. For soil and plants, NH 3 -mediated nitrogen can act as a harmful pollutant or as a desirable nutrient, mostly in natural and agricultural settings, respectively. Agriculture is also the main source of atmospheric NH 3 via volatilization from fertilizers and manure processing in livestock farming. The accurate determination of NH 3 emission rates remains a challenge, partly due to the propensity of NH 3 to interact with instrument surfaces leading to high detection limits and slow response times. In this paper, we present a new method for quantifying ambient NH 3 , using chemical ionization mass spectrometry (CIMS) with deuterated benzene cations as reagents. The setup aimed at limiting sample-surface interactions and achieved a 1-σ precision of 10–20 pptv and an immediate 1/e response rate < 0.4 s, which compares favorably to the existing state of the art. The sensitivity exhibited an inverse humidity dependence, in particular in relatively dry conditions. Background of up to 10 % of the total signal required consideration as well, as it responded on the order of a few minutes. To showcase the method’s capabilities, we quantified NH3 mixing ratios from measurements obtained during deployment on a Gulfstream I aircraft during the HI-SCALE (Holistic Interactions of Shallow Clouds, Aerosols and Land Ecosystems) field campaign in rural Oklahoma during May 2016. Typical mixing ratios were 1–10 parts per billion by volume (ppbv) for the boundary layer and 0.1–1 ppbv in the lower free troposphere. Sharp plumes of up to 10s of ppbv of NH3 were encountered as well. We identified two of their sources as a large fertilizer plant and a cattle farm, and our mixing ratio measurements yielded upper bounds of 350 ± 50 and 0.6 kg NH 3 h –1 for their respective momentary source rates. The fast response of the CIMS also allowed us to derive vertical NH 3 fluxes within the turbulent boundary layer via eddy covariance, for which we chiefly used the continuous wavelet transform technique. As expected for a region dominated by agriculture, we observed predominantly upward fluxes, implying net NH 3 emissions from surface. The corresponding analysis focused on the most suitable flight, which contained two straight-and-level legs at ~300 m above ground. We derived NH 3 fluxes between –4 and 18 mol km –2 h –1 for these legs, at an effective spatial resolution of 1–2 km. The analysis demonstrated how flux measurements benefit from suitably arranged flight tracks with sufficiently long straight-and-level legs, and explores the detrimental effect of measurement discontinuities. Following flux footprint estimations, comparison to the NH 3 area emissions inventory provided by the US Environmental Protection Agency indicated overall agreement, but also the absence of some sources, for instance the identified cattle farm. Our study concludes that high-precision CIMS measurements are a powerful tool for in-situ measurements of ambient NH 3 mixing ratios, and even allow for the airborne mapping of the air-surface exchange of NH 3 .

54 ENVIRONMENTAL SCIENCES↗

Airborne flux measurements of ammonia over the southern Great Plains using chemical ionization mass spectrometry

Abstract. Ammonia (NH3) is an abundant trace gas in the atmosphere and an important player in atmospheric chemistry, aerosol formation and the atmosphere–surface exchange of nitrogen. The accurate determination of NH3 emission rates remains a challenge, partly due to the propensity of NH3 to interact with instrument surfaces, leading to high detection limits and slow response times. In this paper, we present a new method for quantifying ambient NH3, using chemical ionization mass spectrometry (CIMS) with deuterated benzene cations as reagents. The setup aimed at limiting sample–surface interactions and achieved a 1σ precision of 10–20 pptv and an immediate 1/e response rate of < 0.4 s, which compares favorably to the existing state of the art. The sensitivity exhibited an inverse humidity dependence, in particular in relatively dry conditions. Background of up to 10 % of the total signal required consideration as well, as it responded on the order of a few minutes. To showcase the method's capabilities, we quantified NH3 mixing ratios from measurements obtained during deployment on a Gulfstream I aircraft during the HI-SCALE (Holistic Interactions of Shallow Clouds, Aerosols, and Land-Ecosystems) field campaign in rural Oklahoma during May 2016. Typical mixing ratios were 1–10 parts per billion by volume (ppbv) for the boundary layer and 0.1–1 ppbv in the lower free troposphere. Sharp plumes of up to tens of ppbv of NH3 were encountered as well. We identified two of their sources as a large fertilizer plant and a cattle farm, and our mixing ratio measurements yielded upper bounds of 350 ± 50 and 0.6 kg NH3 h−1 for their respective momentary source rates. The fast response of the CIMS also allowed us to derive vertical NH3 fluxes within the turbulent boundary layer via eddy covariance, for which we chiefly used the continuous wavelet transform technique. As expected for a region dominated by agriculture, we observed predominantly upward fluxes, implying net NH3 emissions from the surface. The corresponding analysis focused on the most suitable flight, which contained two straight-and-level legs at ∼ 300 m above ground. We derived NH3 fluxes between 1 and 11 mol km−2 h−1 for these legs, at an effective spatial resolution of 1–2 km. The analysis demonstrated how flux measurements benefit from suitably arranged flight tracks with sufficiently long straight-and-level legs, and it explores the detrimental effect of measurement discontinuities. Following flux footprint estimations, comparison to the NH3 area emissions inventory provided by the U.S. Environmental Protection Agency indicated overall agreement but also the absence of some sources, for instance the identified cattle farm. Our study concludes that high-precision CIMS measurements are a powerful tool for in situ measurements of ambient NH3 mixing ratios, and even allow for the airborne mapping of the air–surface exchange of NH3.

58 GEOSCIENCES↗

Measurements of Halogenated Organic Compounds near the Tropical Tropopause

The amount of organic chlorine and bromine entering the stratosphere have a direct influence on the magnitude of chlorine and bromine catalyzed ozone losses. Twelve organic chlorine species and five organic bromine species were measured from 12 samples collected near the tropopause between 23.8 deg N and 25.3 deg N during AASE 2. The average mixing ratios of total organic chlorine and total organic bromine were 3.50 +/- 0.06 ppbv and 21.1 +/- 0.8 pptv, respectively. CH3Cl represented 15.1% of the total organic chlorine, with CFC 11 (CCl3F) and CFC 12 (CCl2F2) accounting for 22.6% and 28.2%, respectively, with the remaining 34.1% primarily from CCl4, CH3CCl3, and CFC 113 (CCl2FCClF2). CH3Br represented 54% of the total organic bromine. The 95% confidence intervals of the mixing ratios of all but four of the individual compounds were within the range observed in low and mid-latitude midtroposphere samples. The four compounds with significantly lower mixing ratios at the tropopause were CHCl3, CH2Cl2, CH2Br2, and CH3CCl3. The lower mixing ratios may be due to entrainment of southern hemisphere air during vertical transport in the tropical region and/or to exchange of air across the tropopause between the lower stratosphere and upper troposphere.

Schauffler, S. M.↗

Measurements of halogenated organic compounds near the tropical tropopause

The amount of organic chlorine and bromine entering the stratosphere have a direct influence on the magnitude of chlorine and bromine catalyzed ozone losses. Twelve organic chlorine species and five organic bromine species were measured from 12 samples collected near the tropopause between 23.8 deg N and 25.3 deg N during AASE 2. The average mixing ratios of total organic chlorine and total organic bromine were 3.50 +/- 0.06 ppbv and 21.1 +/- 0.8 pptv, respectively. CH3Cl represented 15.1% of the total organic chlorine, with CFC 11 (CCl3F) and CFC 12 (CCl2F2) accounting for 22.6% and 28.2%, respectively, with the remaining 34.1% primarily from CCl4, CH3CCl3, and CFC 113 (CCl2FCClF2). CH3Br represented 54% of the total organic bromine. The 95% confidence intervals of the mixing ratios of all but four of the individual compounds were within the range observed in low and mid-latitude mid-troposphere samples. The four compounds with significantly lower mixing ratios at the tropopause were CHCl3, CH2Cl2, CH2Br2, and CH3CCl3. The lower mixing ratios may be due to entrainment of southern hemisphere air during vertical transport in the tropical region and/or to exchange of air across the tropopause between the lower stratosphere and upper troposphere.

Schauffler, S. M.↗

Compact Reconnaissance Imaging Spectrometer Observations of Water Vapor and Carbon Monoxide

The Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) onboard the Mars Reconnaissance Orbiter (MRO) spacecraft began taking observations in September 2006 and has now collected more than a full Martian year of data. Retrievals performed using the near-infrared spectra obtained by CRISM are used to characterize the seasonal and spatial variation of the column abundance of water vapor and the column-averaged mixing ratio of carbon monoxide. CRISM retrievals show nominal behavior in water vapor during northern hemisphere spring and summer with maximum abundance reaching 50 precipitable micrometers. Water vapor abundance during the southern hemisphere spring and summer appears significantly reduced compared to observations by other instruments taken during previous years. The CRISM retrievals show the seasonally and globally averaged carbon monoxide mixing ratio to be 700 ppm, but with strong seasonal variations at high latitudes. The summertime near-polar carbon monoxide mixing ratio falls to 200 ppm in the south and 400 ppm in the north as carbon dioxide sublimates from the seasonal polar ice caps and dilutes noncondensable species including carbon monoxide. At low latitudes, the carbon monoxide mixing ratio varies in response to the mean seasonal cycle of surface pressure.

Smith, Michael D.↗

Numerical simulation of life cycles of advection warm fog

The formation, development and dissipation of advection warm fog is investigated. The equations employed in the model include the equation of continuity, momentum and energy for the descriptions of density, wind component and potential temperature, respectively, together with two diffusion equations for the modification of water-vapor mixing ratio and liquid-water mixing ratios. A description of the vertical turbulent transfer of heat, moisture and momentum has been taken into consideration. The turbulent exchange coefficients adopted in the model are based on empirical flux-gradient relations.

Hung, R. J.↗

Retrieval of thermodynamic variables with deep convective clouds Experiments in three dimensions

A three-dimensional numerical cloud model has been used to test a method for retrieving temperature and pressure deviation fields from detailed wind and water fields in deep convective clouds. A comparison of the retrieved fields with the output from the numerical model was used to test the validity of the theoretical treatment and accuracy of the programming. The local time derivatives of each of the velocity components are known to be potential problem sources in using Doppler radar data, and a test was done with this derivative estimated over a 4 min time span rather than 30 s, resulting in excellent agreement with the original solution for this data set. When the local derivative was eliminated, the solution was judged useful for general temperature patterns. Errors due to the inability to measure cloudwater mixing ratio and inaccuracies in rainwater mixing ratio were found to be significant, but not so severe as in the turbulence and steady-state sensitivity tests.

Hane, C. E.↗

Mesospheric water vapor measurements from Penn State - Monthly mean observations (1984-1987)

Mesospheric water vapor measurements obtained by ground-based microwave spectroscopy between November 1984 and July 1987 are examined. Monthly mean water vapor profiles are used to establish annual and interannual variability. The results suggest that the seasonal variation of upper mesospheric water vapor is dominated by an annual component with low mixing ratios in winter and high mixing ratios in summer. The results are compared with those reported by Bevilacqua et al. (1987).

Bevilacqua, Richard M.↗

Analysis of Atmospheric Conditions Responsible for an Ozone Exceedance Event in Southeast Virginia on June 15, 2022

On June 15, 2022, the Virginia Department of Environmental Quality monitoring site at Suffolk/Holland, a rural site in southeast Virginia, recorded its first ozone exceedance since 2016. An ozone exceedance day occurs when the daily maximum 8-hour average surface ozone concentration is greater than 70 ppb. On this day, it was 75 ppb. This event is also noteworthy due to the rapid increase in surface ozone between 6 am and 9 am EDT as well as the hourly maximum ozone concentration of 82 ppb that was measured at 1 pm EDT. In this analysis, we utilize various observational and model data to determine the atmospheric conditions responsible for this ozone exceedance event. The analysis is conducted in two parts: (1) an evaluation of the accuracy of the GEOS-CF and WRF-Chem model forecasts and (2) an investigation of the mechanisms responsible for the high surface ozone at the Virginia DEQ Suffolk/Holland monitoring site. Comparisons of model forecasted ozone time-height cross sections with measured ozone by lidars from the Tropospheric Ozone Lidar Network (TOLNet) at NASA Langley and NASA Goddard reveal that both models forecasted ozone reasonably well near the surface. Model and observational data reveal that an upper-level ridge was present over much of the eastern United States, with a broad anticyclonic circulation near the surface, resulting in north-northeasterly flow over southeast Virginia. Back trajectory calculations using the Hybrid Single-Particle Lagrangian Integrated Trajectory model (HYSPLIT) and model data suggest that a low-level plume rich in ozone and precursor species originating from the New York City and New Jersey region was transported along the east coast between June 14 and June 15, arriving in southeast Virginia around 6 am EDT on June 15. In the early morning hours, this plume mixed down to the surface, elevating the background ozone mixing ratio as well as the mixing ratios of several precursor species. Other potential contributions are also explored and discussed. Lastly, the authors note that this work represents the analysis of the authors and not the Virginia Department of Environmental Quality.

Daniel B Phoenix↗

Stratospheric water vapor variability for Washington, DC/Boulder, CO - 1964-82

Measurements for Washington, DC and Boulder, CO are combined to provide a time series of midlatitude stratospheric water vapor data for the period 1964-82. The mean concentration for the data period is shown to be nearly constant with altitude for the low stratospheric layer between 16-22 km with a mass mixing ratio for the layer of 2.5-2.6 ppmm. Above 22 km the mixing ratio increases slightly with altitude. Evident in the 60 mb level time series is an annual cycle, a quasi-biennial cycle and a long-term nonlinear trend. The quasi-biennial cycle in water vapor at midlatitudes is consistent with variations in tropical stratosphere zonal winds and temperature and total ozone and suggests a modulation of the Hadley cell circulation. The long-term trend shows mixing ratio increasing during the 1960s and decreasing in the 1970s after 1972.

Mastenbrook, H. J.↗

Seasonal Variations in Atmospheric Composition as Measured in Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument onboard the Mars Science Laboratory Curiosity rover measures the chemical composition of major atmospheric species (CO2, N2, 40Ar,O2, and CO) through a dedicated atmospheric inlet. We report here measurements of volume mixing ratios in Gale Crater using the SAM quadrupole mass spectrometer, obtained over a period of nearly 5 years (3 Mars years) from landing. The observation period spans the northern summer of MY31 and solar longitude (L(sub S)) of 175° through spring of MY 34, L(sub S) = 12°. This work expands upon prior reports of the mixing ratios measured by SAM QMS in the first 105 sols of the mission. The SAM QMS atmospheric measurements were taken periodically, with a cumulative coverage of four or five experiments per season on Mars. Major observations include the seasonal cycle of CO2, N2, and Ar, which lags approximately 20–40° of L(sub S) behind the pressure cycle driven by CO2 condensation and sublimation from the winter poles. This seasonal cycle indicates that transport occurs on faster timescales than mixing. The mixing ratio of O2 shows significant seasonal and interannual variability, suggesting an unknown atmospheric or surface process at work. The O2 measurements are compared to several parameters, including dust optical depth and trace CH4 measurements by Curiosity. We derive annual mean volume mixing ratios for the atmosphere in Gale Crater: CO2 = 0.951 (±0.003), N2 = 0.0259 (±0.0006), 40Ar = 0.0194 (±0.0004), O2 = 1.61 (±0.09) x 10(exp ‐3), and CO = 5.8 (±0.8) x 10(exp ‐4).

Gale Crater↗

H2O-H2SO4 system in Venus' clouds and OCS, CO, and H2SO4 profiles in Venus' troposphere

A coupled problem of diffusion and condensation is solved for the H2SO4-H2O system in Venus' cloud layer. The position of the lower cloud boundary and profiles of the H2O and H2SO4 vapor mixing ratios and of the H2O/H2SO4 ratio of sulfuric acid aerosol and its flux are calculated as functions of the column photochemical production rate of sulfuric acid, Phi(sub H2SO4). Variations of the lower cloud boundary are considered. Our basic model, which is constrained to yield f(sub H2O) (30 km) = 30 ppm (Pollack et al. 1993), predicts the position of the lower cloud boundary at 48.4 km coinciding with the mean Pioneer Venus value, the peak H2SO4 mixing ratio of 5.4 ppm, and the H2SO4 production rate Phi(sub H2SO4) = 2.2 x 10(exp 12)/sq cm/s. The sulfur to sulfuric acid mass flux ratio in the clouds is 1:27 in this model, and the mass loading ratio may be larger than this value if sulfur particles are smaller than those of sulfuric acid. The model suggests that the extinction coefficient of sulfuric acid particles with radius 3.7 micrometers (mode 3) is equal to 0.3/km in the middle cloud layer. The downward flux of CO is equal to 1.7 x 10(exp 12)/sq cm/s in this model. Our second model, which is constrained to yield f(sub H2O) = 10 ppm at the lower cloud boundary, close to the value measured by the Magellan radiooccultations, predicts the position of this boundary to be at 46.5 km, which agrees with the Magellan data; f(sub H2O) (30 km) = 90 ppm, close to the data of Moroz et al. (1983) at this altitude; Phi(sub H2SO4) = 6.4 x 10(exp 12)/sq cm/s; and Phi(sub co) = 4.2 x 10(exp 12)/sq cm/s. The S/H2SO4 flux mass ratio is 1:18, and the extinction coefficient of the mode 3 sulfuric acid particles is equal to 0.9 km in the middle cloud layer. A strong gradient of the H2SO4 vapor mixing ratio near the bottom of the cloud layer drives a large upward flux of H2SO4, which condenses and forms the excessive downward flux of liquid sulfuric acid, which is larger by a factor of 4-7 than the flux in the middle cloud layer. This is the mechanism of formation of the lower cloud layer. Variations of the lower cloud layer are discussed. Our modeling of the OCS and CO profiles in the lower atmosphere measured by Pollack et al. (1993) provides a reasonable explanation of these data and shows that the rate coefficient of the reaction SO3 + CO yields CO2 + SO2 is equal to 10(exp -11) exp(-(13,100 +/- 1000)/T) cc/s. The main channel of the reaction between SO3 and OCS is CO2 + (SO)2, and its rate coefficient is equal to 10(exp -11) exp(-(8900 +/- 500)/T) cc/s. In the conditions of Venus' lower atmosphere, (SO)2 is removed by the reaction (SO)2 + OCS yields CO + S2 + SO2. The model predicts an OCS mixing ratio of 28 ppm near the surface.

Krasnopolsky, V. A.↗

SAGE observations of stratospheric nitrogen dioxide

The global distribution of nitrogen dioxide in the middle to upper stratosphere (25-45 km altitude) for the period February 1979 to November 1981 has been determined from observations of attenuated solar radiation in the visible region 0.385-0.45 micron by the Stratospheric Aerosol and Gas Experiment (SAGE) satellite instrument. The SAGE-derived NO2 vertical profiles compare well with observations by balloon- and aircraft-borne sensors. The global SAGE NO2 distributions generally show a maximum in mixing ratio of 8 parts per billion by volume at about 35 km altitude near the equatorial latitudes at local sunset. The location of the mixing ratio peak moves synchronously with the overhead sun for the four different seasons. High-latitude NO2 column content shows strong seasonal variation, with a maximum in local summer and a minimum in local winter. Selected data at high-latitude winter seasons are presented, suggesting that the large variation shown could be explained by the coupling of both dynamics and photochemistry of the NO(x) species. Finally, profiles of the ratio of sunset to sunrise NO2 mixing ratios, peaking at about a factor of two at 30 km, are shown.

Chu, W. P.↗

Vertical profiles of CO and CH4 in the lower and middle troposphere over the Eastern United States January 1978

Samples of tropospheric air were obtained over the Eastern United States during January of 1978. These samples were analyzed by gas chromatography using flame ionization detection to produce vertical profiles of carbon monoxide and methane from the surface to 8 km. The carbon monoxide mixing ratios at 35 deg N and 45 deg N agree with previously published values; however, the mixing ratio at 25 deg N was significantly lower than most published values. The methane mixing ratio was weakly dependent on latitude and has an average value of 1.64 ppm.

Reichle, H. G., Jr.↗

An intercomparison of nitric oxide measurement techniques

Results from an intercomparison of techniques to measure tropospheric levels of nitric oxide (NO) are discussed. The intercomparison was part of the National Aeronautics and Space Administration's Global Tropospheric Experiment and was conducted at Wallops Island, VA, in July 1983. Instruments intercompared included a laser-induced fluorescence system and two chemiluminescence instruments. The intercomparisons were performed with ambient air at NO mixing ratios ranging from 10 to 60 pptv and NO-enriched ambient air at mixing ratios from 20 to 170 pptv. All instruments sampled from a common manifold. The techniques exhibited a high degree of correlation among themselves and with changes in the NO mixing ratio. Agreement among the three techniques was placed at approximately + or - 30 percent. Within this level of agreement, no artifacts or species interferences were identified.

Hoell, J. M., Jr.↗