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At least 127 records · Page 7

Detection of SO2 in the UV spectrum of Venus

The broad absorption feature below 3300 A in the Venus UV spectrum is identified as primarily due to SO2 absorption based on new higher resolution spectra of the 3000-3400 A region showing broad (10 A), unresolved absorptions in the regions at all SO2 band origins between 3000 and 3300 A. SO2 mixing ratios vary from 5 x 10 to the -7th down to an upper limit of 2 x 10 to the -8th at a phase angle of 138 deg. Previous observational determinations of the SO2 mixing ratio were biased toward large phase angles, and consequently did not detect any SO2 absorption at the 10 to the -8th level. The upper limit derived from the CS2 band head at 3206 A is not greater than 5 x 10 to the -8th. The observed range of SO2 mixing ratios is consistent with model predictions based on the sulfur photochemistry at the cloud tops. Ground-based observations of SO2 mixing ratio will provide constraints on models and check on the Venera and Pioneer Venus measurements of the mixing ratios of SO2 and other sulfur-bearing gases with altitude.

Barker, E. S.↗

Ground-based measurements of water vapor in the middle atmosphere

We present measurements of the middle atmospheric water vapor mixing ratio profile obtained using the ground-based Naval Research Laboratory (NRL) water vapor millimeter-wave spectrometer (WVMS) instrument at the Jet Propulsion Laboratory (JPL) Table Mountain Observatory. The measurements cover a period of 262 days from January 23, 1992, to October 13, 1992. During this campaign it was possible to retrieve useful daily mixing ratio profiles for 186 days. We thus have a nearly continuous record of water vapor mixing ratios for altitudes from approximately equals 35 to 75 km. The retrievals are obtained using the optimal estimation method. Details of the error analysis are presented, and a technique is introduced that reduces baseline effects and helps to estimate the baseline error. The high-altitude (greater than or approx. equal to 65 km) data show a sharp rise prior to the expected maximum near the summer solstice and a gradual decline in the following months. The mixing ratios generally peak between 55 and 65 km, at which point the mixing ratios are 6 - 7 parts per million by volume. The highest peaks occur in January, May, and October.

Nedoluha, Gerald E.↗

Nitric oxide profile from 7 to 32 km

An analysis is given of some results of the LIMS experiment, launched on the Nimbus 7 satellite on October 24, 1978 for the purpose of sounding the middle atmosphere composition and structure. One of the LIMS channels was centered spectrally in the 6 micron region to measure vertical profiles and the global distribution of NO2 mixing ratio. The data reveal that NO2 is highly variable with altitude, latitude, longitude and time. Steep latitudinal gradients are observed in high latitude winter ('the NO2 cliff') when a wave number one pattern exists in the geopotential height field. The daytime gradient under these conditions is less than that for the night. The summer hemisphere column amount is considerably greater (by a factor of about 2) than in the winter hemisphere. The largest mixing ratios occur at 4 mb at night (about 20 ppbv) and 9 mb in the day (about 7 ppbv) and the latitude region of the peak mixing ratio is skewed toward the Southern Hemisphere. The mixing ratio variability is greater at night (by a factor of about 2 to 3) than in the day and there are significant long-term changes revealed by mixing ratio time series analyses on a pressure vs time grid.

Matthews, W. A.↗

Comparison of Sub-Ppm Instrument Response Suggests Higher Detection Limits Could Be Used to Quantify Methane Emissions from Oil and Gas Infrastructure

Quantifying and controlling fugitive methane emissions from oil and gas facilities remains essential for addressing climate goals, but the costs associated with monitoring millions of production sites remain prohibitively expensive. Current thinking, supported by measurement and simple dispersion modelling, assumes single-digit parts-per-million instrumentation is required. To investigate instrument response, the inlets of three trace-methane (sub-ppm) analyzers were collocated on a facility designed to release gas of known composition at known flow rates between 0.4 and 5.2 kg CH 4 h –1 from simulated oil and gas infrastructure. Methane mixing ratios were measured by each instrument at 1 Hertz resolution over nine hours. While mixing ratios reported by a cavity ring-down spectrometer (CRDS)-based instrument were on average 10.0 ppm (range 1.8 to 83 ppm), a mid-infrared laser absorption spectroscopy (MIRA)-based instrument reported short-lived mixing ratios far larger than expected (range 1.8 to 779 ppm) with a similar nine-hour average to the CRDS (10.1 ppm). We suggest the peaks detected by the MIRA are likely caused by a micrometeorological phenomenon, where vortex shedding has resulted in heterogeneous methane plumes which only the MIRA can observe. Further analysis suggests an instrument like the MIRA (an optical-cavity-based instrument with cavity size ≤10 cm3 measuring at ≥2 Hz with air flow rates in the order of ≤0.3 slpm at distances of ≤20 m from the source) but with a higher detection limit (25 ppm) could detect enough of the high-concentration events to generate representative 20 min-average methane mixing ratios. Even though development of a lower-cost, high-precision, high-accuracy instrument with a 25 ppm detection threshold remains a significant problem, this has implications for the use of instrumentation with higher detection thresholds, resulting in the reduction in cost to measure methane emissions and providing a mechanism for the widespread deployment of effective leak detection and repair programs for all oil and gas infrastructure.

03 NATURAL GAS↗

Numerical simulation of flow and mixing in fracture intersections

Fluid transport through fractured geological formations is strongly influenced by the redistribution of solutes at fracture intersections. In this study, we perform detailed numerical simulations of flow and scalar transport within the intersection of two smooth, planar fractures. The analysis focuses on the mixing ratio, the proportion of solute flux exiting along the outlet branch aligned with the primary inlet flow direction, relative to the total solute flux at the outlets. We systematically investigate how the mixing ratio varies with four key parameters: Peclet number, Reynolds number, flow rate ratio between outlet branches, and fracture intersection angle. Results show that the mixing ratio decreases with increasing Peclet number and outlet flow rate ratio, consistent with reduced diffusive spreading and enhanced streamline routing. While low Reynolds numbers have minimal impact, inertial effects at higher Reynolds numbers significantly increase the mixing ratio. Additionally, acute and obtuse intersection angles alter flow partitioning and modify the solute distribution at the outlets. These findings provide a quantitative basis for incorporating physically realistic mixing behavior—intermediate between complete mixing and streamline-following assumptions—into network-scale transport models. The results have direct relevance to subsurface energy systems, including geothermal energy production, carbon sequestration, and contaminant remediation.

58 GEOSCIENCES↗

An Earth longwave radiation climate model

An Earth outgoing longwave radiation (OLWR) climate model was constructed for radiation budget study. Required information is provided by on empirical 100mb water vapor mixing ratio equation of the mixing ratio interpolation scheme. Cloud top temperature is adjusted so that the calculation would agree with NOAA scanning radiometer measurements. Both clear sky and cloudy sky cases are calculated and discussed for global average, zonal average and world-wide distributed cases. The results agree well with the satellite observations. The clear sky case shows that the OLWR field is highly modulated by water vapor, especially in the tropics. The strongest longitudinal variation occurs in the tropics. This variation can be mostly explained by the strong water vapor gradient. Although in the zonal average case the tropics have a minimum in OLWR, the minimum is essentially contributed by a few very low flux regions, such as the Amazon, Indonesian and the Congo.

Yang, S. K.↗

The Volatile Composition of the Inner Coma of Comet 46P/Wirtanen: Coordinated Observations Using iSHELL at the NASA-IRTF and Keck/NIRSPEC-2

The 2018 perihelion passage of comet 46P/Wirtanen afforded an opportunity to measure the abun-dances and spatial distributions of coma volatiles in a Jupiter-family comet with exceptional spatialresolution for several weeks surrounding its closest approach to Earth (∆min∼0.078 au on UT Decem-ber 16). We conducted near-infrared spectroscopic observations of 46P/Wirtanen using iSHELL at theNASA Infrared Telescope Facility on UT 2018 December 18 in direct coordination with observations using the newly upgraded NIRSPEC-2 instrument at the W. M. Keck Observatory, and securely de-tected fluorescent emission from CH3OH, C2H6, and H2O. This coordinated campaign utilizing the twopremier near-infrared facilities in the northern hemisphere enabled us to sample distinct projections ofthe coma into the plane of the sky simultaneously, and provided an unprecedented view into the innercoma of 46P/Wirtanen near closest approach. We report rotational temperatures, production rates,and abundance ratios (i.e., mixing ratios) for all sampled species and compare ouriSHELLresultsto simultaneous (or near-simultaneous) measurements taken with NIRSPEC-2. We demonstrate theextraordinary synergy of coordinated measurements using iSHELL and NIRSPEC-2, and advocate forfuture cometary studies that jointly leverage the capabilities of these two facilities.

Molecular spectroscopy;↗

The Volatile Composition of the Inner Coma of Comet 46P/Wirtanen: Coordinated Observations Using iSHELL at the NASA-IRTF and Keck/NIRSPEC-2

The 2018 perihelion passage of comet 46P/Wirtanen afforded an opportunity to measure the abundances andspatial distributions of coma volatiles in a Jupiter-family comet with exceptional spatial resolution for severalweeks surrounding its closest approach to Earth(Δmin∼0.078 au on UT December 16). We conducted near-infrared spectroscopic observations of 46P/Wirtanen using iSHELL at the NASA Infrared Telescope Facility onUT 2018 December 18 in direct coordination with observations using the newly upgraded NIRSPEC-2 instrumentat the W. M. Keck Observatory, and securely detectedfluorescent emission from CH3OH, C2H6, and H2O. Thiscoordinated campaign utilizing the two premier near-infrared facilities in the northern hemisphere enabled us tosample distinct projections of the coma into the plane of the sky simultaneously, and provided an unprecedentedview into the inner coma of 46P/Wirtanen near closest approach. We report rotational temperatures, productionrates, and abundance ratios(i.e., mixing ratios)for all sampled species and compare our iSHELL results tosimultaneous(or near-simultaneous)measurements taken with NIRSPEC-2. We demonstrate the extraordinarysynergy of coordinated measurements using iSHELL and NIRSPEC-2, and advocate for future cometary studiesthat jointly leverage the capabilities of these two facilities.

Nathaniel X Roth↗

The Volatile Composition of the Inner Coma of Comet 46P/Wirtanen: Coordinated Observations Using iSHELL at the NASA-IRTF and Keck/NIRSPEC-2

The 2018 perihelion passage of comet 46P/Wirtanen afforded an opportunity to measure the abundances and spatial distributions of coma volatiles in a Jupiter-family comet with exceptional spatial resolution for several weeks surrounding its closest approach to Earth (Δ(min) ~0.078 au on UT December 16). We conducted near-infrared spectroscopic observations of 46P/Wirtanen using iSHELL at the NASA Infrared Telescope Facility on UT 2018 December 18 in direct coordination with observations using the newly upgraded NIRSPEC-2 instrument at the W. M. Keck Observatory, and securely detected fluorescent emission from CH3OH, C2H6, and H2O. This coordinated campaign utilizing the two premier near-infrared facilities in the northern hemisphere enabled us to sample distinct projections of the coma into the plane of the sky simultaneously, and provided an unprecedented view into the inner coma of 46P/Wirtanen near closest approach. We report rotational temperatures, production rates, and abundance ratios (i.e., mixing ratios) for all sampled species and compare our iSHELL results to simultaneous (or near-simultaneous) measurements taken with NIRSPEC-2. We demonstrate the extraordinary synergy of coordinated measurements using iSHELL and NIRSPEC-2, and advocate for future cometary studies that jointly leverage the capabilities of these two facilities.

Nathaniel X. Roth↗

Large-Scale Distributions of Tropospheric Nitric, Formic, and Acetic acids Over the Westerm Pacific Basin During Wintertime

We report here measurements of the acidic gases nitric (HNO3), formic (HCOOH), and acetic (CH3COOH) over the western Pacific basin during the February-March 1994 Pacific Exploratory Mission-West (PEM-West B). These data were obtained aboard the NASA DC-8 research aircraft as it flew missions in the altitude range of 0.3 - 12.5 km over equatorial regions near Guam and then further westward encompassing the entire Pacific Rim arc. Aged marine air over the equatorial Pacific generally exhibited mixing ratios of acidic gases less than 100 parts per trillion by volume (pptv). Near the Asian continent, discrete plumes encountered below 6 km altitude contained up to 8 parts per billion by volume (ppbv) HNO3 and 10 ppbv HCOOH and CH3COOH. Overall there was a general correlation between mixing ratios of acidic gases with those of CO, C2H2, and C2Cl4, indicative of emissions from combustion and industrial sources. The latitudinal distributions of HNO3 and CO showed that the largest mixing ratios were centered around 15 deg N, while HCOOH, CH3COOH, and C2Cl4 peaked at 25 deg N. The mixing ratios of HCOOH and CH3COOH were highly correlated (r(sup 2) = 0.87) below 6 km altitude, with a slope (0.89) characteristic of the nongrowing season at midlatitudes in the northern hemisphere. Above 6 km altitude, HCOOH and CH3COOH were marginally correlated (r(sup 2) = 0.50), and plumes well defined by CO, C2H2, and C2Cl4 were depleted in acidic gases, most likely due to scavenging during vertical transport of air masses through convective cloud systems over the Asian continent. In stratospheric air masses, HNO, mixing ratios were several parts per billion by volume (ppbv), yielding relationships with 03 and N2O consistent with those previously reported for NO(y).

Talbot, R. W.↗

SPARC-IGAC Symposium on Climate-Chemistry Interactions. Climate Feedback by Water Vapor in the Tropical Upper Troposphere

The strong greenhouse forcing by atmospheric water vapor is expected to play an important role in shaping the direction of any future changes in climate. We present calculations that provide a new perspective on the sensitivity of upper tropospheric water vapor to changes in surface temperature. Equilibrium states of our atmospheric model show unambiguously that as the surface warms, changes in the vertical distribution and temperature of detraining air parcels from tropical convection lead to higher water vapor mixing ratios in the upper troposphere. However, the increase in mixing ratio is not as large as the increase in saturation mixing ratio due to warmer environmental temperatures, so that the relative humidity decreases. Our analysis suggests that models that maintain a fixed relative humidity are likely overestimating the magnitude of the water vapor feedback.

Dessler, A. E.↗

Quantitative observations of the behavior of anomalous low altitude ClO in the Antarctic spring Stratosphere, 1987

During the second National Ozone Expedition ground-based observations at McMurdo Station Antarctica were performed which resulted in a second season's measurement of abnormally large amounts of ClO in the Antarctic spring stratosphere. The original measurements of 1986, in which the presence of this anomalous layer was first discovered, were limited in low altitude recovery of the ClO mixing ratio profile by the restrictions of the spectral bandwidth (256 MHz) which was used to measure the pressure-broadened ClO emission line shape. The 1987 measurements were marked by the use of twice the spectral bandpass employed the previous year, and allow a better characterization of the ClO mixing ratio profile in the critical altitude range 18 to 25 km. In-situ aircraft measurements of ClO made over the Palmer Peninsula during Aug. and Sept. of 1987 by Anderson, et al. effectively determined the important question of the ClO mixing ratio profile at altitudes inaccessible to our technique, below approximately 18 to 18.5 km. These flights did not penetrate further than 75 deg S, however, (vs 78 deg S for McMurdo) and were thus limited to coverage near the outer boundaries of the region of severest ozone depletion over Antarctica in 1987, did not reach an altitude convincingly above that of the peak mixing ratio for ClO, and were not able to make significant observations of the diurnal variation of ClO. The two techniques, and the body of data recovered by each, thus complement one another in producing a full picture of the anomalous ClO layer intimately connected with the region of Antarctic spring ozone depletion. An analysis is presented of the mixing ratio profile from approximately 18 to 45 km, the diurnal behavior, and the secular change in ClO over McMurdo Station during Sept. and early Oct. 1987.

Dezafra, R. L.↗

Summertime distribution and relations of reactive odd nitrogen species and NO(y) in the troposphere over Canada

We report here large-scale features of the distribution of NO(x), HNO3, PAN, particle NO3, and NO(y) in the troposphere from 0.15 to 6 km altitude over central Canada. These measurements were conducted in July - August 1990 from the NASA Wallops Electra aircraft as part of the joint United States-Canadian Arctic Boundary Layer Expedition (ABLE) 3B-Northern Wetlands Study. Our findings show that this region is generally NO(x) limited, with NO(x) mixing ratios typically 20-30 parts per trillion by volume (pptv). We found little direct evidence for anthropogenic enhancement of mixing ratios of reactive odd nitrogen species and NO(y) above those in 'background' air. Instead, it appears that enhancements in the mixing ratios of these species were primarily due to emissions from several day old or CO-rich-NO(x)-poor smoldering local biomass-burning fires. NO(x) mixing ratios in biomass-burning impacted air masses were usually less than 50 pptv, but those of HNO3 and PAN were typically 100-300 pptv representing a twofold-threefold enhancement over 'background' air. During our study period, inputs of what appeared to be aged tropical air were a major factor influencing the distribution of reactive odd nitrogen in the midtroposphere over northeastern North America. These air masses were quite depleted in NO(y) (generally less than 150 pptv), and a frequent summertime occurrence of such air masses over this region would imply a significant influence on the reactive odd nitrogen budget. Our findings show that the chemical composition of aged air masses over subarctic Canada and those documented in the Arctic during ABLE 3A have strikingly similar chemistries, suggesting large-scale connection between the air masses influencing these regions.

Talbot, R. W.↗

Spectroscopic Detection of COClF in the Tropical and Mid-Latitude Lower Stratosphere

We report retrievals of COClF (carbonyl chlorofluoride) based on atmospheric chemistry experiment (ACE) solar occultation spectra recorded at tropical and mid-latitudes during 2004-2005. The COClF molecule is a temporary reservoir of both chlorine and fluorine and has not been measured previously by remote sensing. A maximum COClF mixing ratio of 99.7+/-48.0 pptv (10(exp -12) per unit volume, 1 sigma) is measured at 28km for tropical and subtropical occultations (latitudes below 20deg in both hemispheres) with lower mixing ratios at both higher and lower altitudes. Northern hemisphere mid-latitude mixing ratios (30-50degN) resulted in an average profile with a peak mixing ratio of 51.7+/-32.1 pptv, 1 sigma, at 27 km, also decreasing above and below that altitude. We compare the measured average profiles with the one reported set of in situ lower stratospheric mid-latitude measurements from 1986 and 1987, a previous two-dimensional (2-D) model calculation for 1987 and 1993, and a 2-D-model prediction for 2004. The measured average tropical profile is in close agreement with the model prediction; the northern mid-latitude profile is also consistent, although the peak in the measured profile occurs at a higher altitude (2.5-4.5km offset) than in the model prediction. Seasonal average 2-D-model predictions of the COClF stratospheric distribution for 2004 are also reported.

Rinsland, Curtis P.↗

Sulfate and nitrate collected by filter sampling near the tropopause

Filter samples collected near the tropopause with an F-106 aircraft and two Boeing 747 aircraft were analyzed for sulfate and nitrate ion content. Within the range of routine commercial flight altitudes (at or below 12.5 km), stratospheric mass mixing ratios for the winter-spring group averaged 0.26 ppbm for sulfate and 0.35 ppbm for nitrate. For the summer-fall group, stratosphere mixing ratios averaged 0.13 ppbm and 0.25 ppbm for sulfate and nitrate, respectively. Winter-spring group tropospheric mass mixing ratios averaged 0.08 ppbm for sulfate and 0.10 ppbm for nitrate, while summer-fall group tropospheric mixing ratios averaged 0.05 ppbm for sulfate and 0.08 ppbm for nitrate. Correlations of the filter data with available ozone data suggest that the sulfate and nitrate are transported from the stratosphere to the troposphere.

Humenik, F. M.↗

Analysis of the Atmospheric Distribution, Sources, and Sinks of Oxygenated Volatile Organic Chemicals Based on Measurements over the Pacific during TRACE-P

Airborne measurements of a large number of oxygenated volatile organic chemicals (OVOC) were carried out in the Pacific troposphere (0.1-12 km) in winter/spring of 2001 (24 February to 10 April). Specifically, these measurements included acetone (CH3COCH3), methylethyl ketone (CH3COC2H5, MEK), methanol (CH3OH), ethanol (C2H5OH), acetaldehyde (CH3CHO), propionaldehyde (C2H5CHO), peroxyacylnitrates (PANs) (C(sub n)H(sub 2n+1)COO2NO2), and organic nitrates (C(sub n)H(sub 2n+1)ONO2). Complementary measurements of formaldehyde (HCHO), methyl hydroperoxide (CH3OOH), and selected tracers were also available. OVOC were abundant in the clean troposphere and were greatly enhanced in the outflow regions from Asia. Background mixing ratios were typically highest in the lower troposphere and declined toward the upper troposphere and the lowermost stratosphere. Their total abundance (Summation of OVOC) was nearly twice that of nonmethane hydrocarbons (Summation of C2-C8 NMHC). Throughout the troposphere, the OH reactivity of OVOC is comparable to that of methane and far exceeds that of NMHC. A comparison of these data with western Pacific observations collected some 7 years earlier (February-March 1994) did not reveal significant differences. Mixing ratios of OVOC were strongly correlated with each other as well as with tracers of fossil and biomass/biofuel combustion. Analysis of the relative enhancement of selected OVOC with respect to CH3Cl and CO in 12 plumes originating from fires and sampled in the free troposphere (3-11 km) is used to assess their primary and secondary emissions from biomass combustion. The composition of these plumes also indicates a large shift of reactive nitrogen into the PAN reservoir thereby limiting ozone formation. A three-dimensional global model that uses state of the art chemistry and source information is used to compare measured and simulated mixing ratios of selected OVOC. While there is reasonable agreement in many cases, measured aldehyde concentrations are significantly larger than predicted. At their observed levels, acetaldehyde mixing ratios are shown to be an important source of HCHO (and HO x ) and PAN in the troposphere. On the basis of presently known chemistry, measured mixing ratios of aldehydes and PANs are mutually incompatible. We provide rough estimates of the global sources of several OVOC and conclude that collectively these are extremely large (150-500 Tg C / yr) but remain poorly quantified.

Singh, H. B.↗

On the Choice of Variable for Atmospheric Moisture Analysis

The implications of using different control variables for the analysis of moisture observations in a global atmospheric data assimilation system are investigated. A moisture analysis based on either mixing ratio or specific humidity is prone to large extrapolation errors, due to the high variability in space and time of these parameters and to the difficulties in modeling their error covariances. Using the logarithm of specific humidity does not alleviate these problems, and has the further disadvantage that very dry background estimates cannot be effectively corrected by observations. Relative humidity is a better choice from a statistical point of view, because this field is spatially and temporally more coherent and error statistics are therefore easier to obtain. If, however, the analysis is designed to preserve relative humidity in the absence of moisture observations, then the analyzed specific humidity field depends entirely on analyzed temperature changes. If the model has a cool bias in the stratosphere this will lead to an unstable accumulation of excess moisture there. A pseudo-relative humidity can be defined by scaling the mixing ratio by the background saturation mixing ratio. A univariate pseudo-relative humidity analysis will preserve the specific humidity field in the absence of moisture observations. A pseudorelative humidity analysis is shown to be equivalent to a mixing ratio analysis with flow-dependent covariances. In the presence of multivariate (temperature-moisture) observations it produces analyzed relative humidity values that are nearly identical to those produced by a relative humidity analysis. Based on a time series analysis of radiosonde observed-minus-background differences it appears to be more justifiable to neglect specific humidity-temperature correlations (in a univariate pseudo-relative humidity analysis) than to neglect relative humidity-temperature correlations (in a univariate relative humidity analysis). A pseudo-relative humidity analysis is easily implemented in an existing moisture analysis system, by simply scaling observed-minus background moisture residuals prior to solving the analysis equation, and rescaling the analyzed increments afterward.

Dee, Dick P.↗

Gaseous constituents in the plume from eruptions of Mount St. Helens

Measurements in the stratosphere of gaseous constituents in the plume of Mount St. Helens were obtained during five flights of the NASA U-2 aircraft between 19 May and 17 June 1980. Mixing ratios from gas chromatographic measurements on samples acquired about 24 hours after the initial eruption show considerable enhancement over nonvolcanic concentrations for sulfur dioxide (more than 1000 times), methyl chloride (about 10 times), and carbon disulfide (more than 3 times). The mixing ratio of carbonyl sulfide was comparable to nonvolcanic mixing ratios although 3 days later it was enhanced two to three times. Ion chromatography measurements on water-soluble constituents are also reported. Very large concentrations of chloride, nitrate, and sulfate ions were measured, implying large mixing ratios for the water-soluble gaseous constituents from which the anions are derived. Measurements of radon-222 present in the plume are also reported.

Inn, E. C. Y.↗