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At least 19 records

A measurement system for the atmospheric trace gases CH4 and CO

A system for measuring ambient clean air levels of the atmospheric trace gases methane and carbon monoxide is described. The analytical method consists of a gas chromatographic technique that incorporates sample preconcentration with catalytic conversion of CO to CH4 and subsequent flame ionization detection of these gases. The system has sufficient sensitivity and repeatability to make the precise measurements required to establish concentration profiles for CO and CH4 in the planetary boundary layer. A discussion of the bottle sampling program being conducted to obtain the samples for the concentration profiles is also presented.

Condon, E. P.↗

Improved aqueous scrubber for collection of soluble atmospheric trace gases

A new concentration technique for the extraction and enrichment of water-soluble atmospheric trace gases has been developed. The gas scrubbing technique efficiently extracts soluble gases from a large volume flow rate of air sample into a small volume of refluxed trapping solution. The gas scrubber utilizes a small nebulizing nozzle that mixes the incoming air with an aqueous extracting solution to form an air/droplet mist. The mist provides excellent interfacial surface areas for mass transfer. The resulting mist sprays upward through the reaction chamber until it impinges upon a hydrophobic membrane that virtually blocks the passage of droplets but offers little resistance to the existing gas flow. Droplets containing the scrubbed gases coalesce on the membrane and drip back into the reservoir for further refluxing. After a suitable concentration period, the extracting solution containing the analyte can be withdrawn for analysis. The nebulization-reflex concentration technique is more efficient (maximum flow of gas through the minimum volume of extractant) than conventional bubbler/impinger gas extraction techniques and is offered as an alternative method.

Cofer, W. R., III↗

Five Decades Observing Earth's Atmospheric Trace Gases Using Ultraviolet and Visible Backscatter Solar Radiation from Space

Over the last five decades, Earth’s atmosphere has been extensively monitored from space using different spectral ranges. Early efforts were directed at improving weather forecasts with the first meteorological satellites launched in the 1960s. Soon thereafter, the intersection between weather, climate and atmospheric chemistry led to the observation of atmospheric composition from space. During the 1970s the Nimbus satellite program started regular monitoring of ozone integrated columns and water vapor profiles using the Backscatter Ultraviolet Spectrometer, the Infrared Interferometer Spectrometer and the Satellite Infrared Spectrometer instruments. Five decades after these pioneer efforts, continuous progress in instrument design, and retrieval techniques allow researchers to monitor tropospheric concentrations of a wide range of species with implications for air quality, climate and weather. The time line of historic, present and future space-borne instruments measuring ultraviolet and visible backscattered solar radiation designed to quantify atmospheric trace gases is presented. We describe the instruments technological evolution and the basic concepts of retrieval theory. We include a review of algorithms developed for ozone, nitrogen dioxide, sulfur dioxide, formaldehyde, bromine monoxide, water vapor and glyoxal, a selection of studies using these algorithms, the challenges they face and how these challenges can be addressed. The paper ends by providing insights on the opportunities that new instruments will bring to the atmospheric chemistry, weather and air quality communities and how to address the pressing need for long-term, inter-calibrated data records necessary to monitor the response of the atmosphere to rapidly changing ecosystems.

Infrared Interferometer Spectrometer↗

Ultrasensitive detection of atmospheric trace gases using frequency modulation spectroscopy

Frequency modulation (FM) spectroscopy is a new technique that promises to significantly extend the state-of-the-art in point detection of atmospheric trace gases. FM spectroscopy is essentially a balanced bridge optical heterodyne approach in which a small optical absorption or dispersion from an atomic or molecular species of interest generates an easily detected radio frequency (RF) signal. This signal can be monitored using standard RF signal processing techniques and is, in principle, limited only by the shot noise generated in the photodetector by the laser source employed. The use of very high modulation frequencies which exceed the spectral width of the probed absorption line distinguishes this technique from the well-known derivative spectroscopy which makes use of low (kHz) modulation frequencies. FM spectroscopy was recently extended to the 10 micron infrared (IR) spectral region where numerous polyatomic molecules exhibit characteristic vibrational-rotational bands. In conjunction with tunable semiconductor diode lasers, the quantum-noise-limited sensitivity of the technique should allow for the detection of absorptions as small as .00000001 in the IR spectral region. This sensitivity would allow for the detection of H2O2 at concentrations as low as 1 pptv with an integration time of 10 seconds.

Cooper, David E.↗

Differential Radiometers Using Fabry-Perot Interferometric Technique for Remote Sensing Determination of Various Atmospheric Trace Gases

New type of remote sensing instrument based upon the Fabry-Perot inte rferometric technique has been developed at NASA's Goddard Space Flight Center. Fabry-Perot interferometry (FPI) is a well known, powerful spectroscopic technique and one of its many applications is to be use d to measure greenhouse gases and also some harmful species in the at mosphere. With this technique, absorption of particular species is me asured and related to its concentration. A solid Fabry-Perot etalon is used as a frequency filter to restrict the measurement to particular absorption bands of the gas of interest. With adjusting the thicknes s of the etalon that separation (in frequency) of the transmitted fri nges can be made equal to the almost constant separation of the gas a bsorption lines. By adjusting the temperature of the etalon, which changes the index of refi-action of its material, the transmission fring es can be brought into nearly exact correspondence with absorption li nes of the particular species. With this alignment between absorption lines and fringes, changes in the amount of a species in the atmosph ere strongly affect the amount of light transmitted by the etalon and can be related to gas concentration. The instrument that we have dev eloped detects the absorption of various atmospheric trace gases in d irect or reflected sunlight. Our instrument employing Fabry-Perot interferometer makes use of two features to achieve high sensitivity. The first is high spectral resolution enabling one to match the width of an atmospheric absorption feature by the instrumental band pass. The second is high optical throughput enabled by using multiple spectral lines simultaneously. For any species that one wishes to measure, thi s first feature is available while the use of multiple spectral features can be employed only for species with suitable spectra and freedom from interfering species in the same wavelength region. We have deve loped an instrument for use as ground based, airborne and satellite s ensor for gases such as carbon dioxide (1570 nm), oxygen (762 nm and 768 nm lines sensitive to changes in oxygen pressure and oxygen temper ature) and water vapor (940 nm). Our current goal is to develop an ul tra precise, inexpensive, ground based device suitable for wide deplo yment as a validation instrument for the Orbiting Carbon Observatory (OCO) satellite. We show sensitivity measurements for CO2, 02, and H2 O, compare our measurements to those obtained using other types of sensors and discuss some of the peculiarities that must be addressed in order to provide the very high quality column detection required for solving problems about global distribution of greenhouse gases and cl imatological models. In another area of research we are interested in developing a small-size channel for CO2 capable of doing simultaneous measurements with the AERONET (Aerosol Robotic Network) at NASA, God dard to study the hypothesis that atmospheric aerosols affect the reg ional terrestrial carbon cycle. We present recent data from our groun d based measurements of O2, CO2, H2O and (13)CO2 and discuss extensio n of the technique to new species and applications.

Georgieva, E. M.↗

Atmospheric trace gases and global climate - A seasonal model study

Atmospheric models with seasonal cycles are used to study the possible near-future changes in latitudinal and vertical distributions of atmospheric ozone and temperature caused by increases of trace gases. It is found that increases of CFCs, CH4, and N2O may add to the surface warming from increased CO2. Calculations based on projected trends of CO2, N2O, CH4, and CFCs show that the annual mean and global mean surface temperature could warm by as much as 2.5 C by the year 2050, with larger warming at high latitudes. The results suggest that the warming in the lower stratosphere and upper troposphere is much larger than that at the surface, especially during the summer season.

Wang, Wei-Chyung↗

Photofragmentation-laser induced fluorescence - A new method for detecting atmospheric trace gases

A new method for the in situ detection of nonfluorescing molecular species is proposed: photofragmentation-laser induced fluorescence (PF-LIF). In this approach, the species to be detected is first laser photolyzed at a wavelength lambda (1), producing one or more vibrationally excited photofragments. Before vibrational relaxation occurs, one of these photofragments is pumped into a bonding excited state by a second laser pulse centered at wavelength lambda (2). Fluorescence is sampled at a wavelength lambda (3), where lambda (3) is less then lambda (2) and lambda (1). This pumping configuration thus permits massive discrimination against Rayleigh and Raman scattering as well as white noise fluorescence from the laser wavelengths lambda (1) and lambda (2). The technique should be both highly sensitive and selective for numerous atmospheric trace gases. Specific sampling schemes for detecting NO2, NO3, and HNO2 are proposed. Various noise sources and chemical interferences are discussed. Specific calculations that estimate the sensitivity of the PF-LIF system for detecting NO2, NO3, and HNO2 are given.

Rodgers, M. O.↗

Open-path tunable diode laser absorption for eddy correlation flux measurements of atmospheric trace gases

Biogenic emissions from and dry deposition to terrestrial surfaces are important processes determining the trace gas composition of the atmosphere. An instrument has been developed for flux measurements of gases such as CH4, N2O, and O3 based on the eddy correlation technique which combines trace gas fluctuation measurements with simultaneous windfield measurements. The instrument combines a tunable diode laser infrared light source with an open-path multipass absorption cell in order to provide the fast time response and short base pathlength required for the eddy correlation method. Initial field tests using the instrument to measure methane emissions from a local wetland demonstrate the capability for high precision eddy correlation flux measurements.

Anderson, Stuart M.↗

Biological cycling of atmospheric trace gases

A detailed critical review was conducted of present knowledge of the influence of biological processes on the cycling of selected atmospheric gas constituents--methane, carbon monoxide, and gaseous compounds of nitrogen (nitrous oxide, ammonia, nitric oxide, and nitrogen dioxide) and sulfur (hydrogen sulfide and sulfur dioxide). The identification was included of biological and other sources of each gas, a survey of abundance measurements reported in the literature, and a review of the atmospheric fate of each contituent. Information is provided on which to base conclusions regarding the importance of biological processes on the atmospheric distribution and surface-atmosphere exchange of each constituent, and a basis for estimating the adequacy of present knowledge of these factors. A preliminary analysis was conducted of the feasibility of monitoring the biologically influenced temporal and spatial variations in abundance of these gases in the atmosphere from satellites.

Hitchcock, D. R.↗

CO2 DIAL sensitivity studies for measurements of atmospheric trace gases

An analysis is presented of the accuracy of infrared differential absorption lidar (DIAL) measurements of trace constituents in the atmosphere. Expressions are derived for the signal-to-noise ratios applicable in the detection of a signal from a scattering cell for the cases of single-detection heterodyne detection and direct detection. Results of computer simulations of the expectation value of the measured return for various measurement conditions are presented which illustrate the sensitivities of plume measurements for horizontal range-resolved and vertical content measurements of NH3 in heterodyne and direct detection. Advantages for long-range measurements of the use of rare isotope laser frequencies, tuning by collision broadening, and closely spaced on and off frequencies are pointed out.

Brockman, P.↗

Miniature Tunable Laser Spectrometers for Quantifying Atmospheric Trace Gases, Water Resources, Earth Back-Contamination, and In Situ Resource Utilization

The Tunable Laser Spectrometers (TLS) technique has seen wide applicability in gas measurement and analysis for atmospheric analysis, industrial, commercial and health monitoring and space applications. In Earth science using balloons and aircraft over 2 decades, several groups (JPL, NASA Langley & Ames, NOAA, Harvard U., etc) have demonstrated the technique for ozone hole studies, lab kinetics measurements, cloud physics and transport, climate change in the ice record. The recent availability of high-power (mW) room temperature lasers (TDL, IC, QC) has enabled miniaturized, high-sensitivity spectrometers for industry and space (1) Mars, Titan, Venus, Saturn, Moon (2) Commercial isotope ratio spectrometers are replacing bulkier, complex isotope ratio mass spectrometers.

Tunable laser spectrometers (TLS)↗

The airborne Laser Absorption Spectrometer - A new instrument of remote measurement of atmospheric trace gases

The Laser Absorption Spectrometer is a portable instrument developed by JPL for remote measurement of trace gases from an aircraft platform. It contains two carbon dioxide lasers, two optical heterodyne receivers, appropriate optics to aim the lasers at the ground and detect the backscattered energy, and signal processing and recording electronics. Operating in the differential-absorption mode, it is possible to monitor one atmospheric gas at a time and record the data in real time. The system can presently measure ozone, ethylene, water vapor, and chlorofluoromethanes with high sensitivity. Airborne measurements were made in early 1977 from the NASA/JPL twin-engine Beechcraft and in May 1977 from the NASA Convair 990 during the ASSESS-II Shuttle Simulation Study. These flights resulted in measurements of ozone concentrations in the lower troposphere which were compared with ground-based values provided by the Air Pollution Control District. This paper describes the details of the instrument and results of the airborne measurements.

Shumate, M. S.↗

Fourier Transform Infrared (FT-IR) Spectroscopy of Atmospheric Trace Gases HCl, NO and SO2

Fourier Transform Infrared (FT-IR) spectral data have been recorded in the spectral region 400-4000/cm of hydrogen chloride and sulfur dioxide with I/cm resolution and of nitric oxide with 0.25 cm-i resolution, under quasi-static conditions, when the sample gas was passed through tubings of aluminum, copper, stainless steel and teflon. The absorbance was measured for the rotational lines of the fundamental bands of (1)H(35)Cl and (1)H(37)Cl for pressures in the range 100-1000 Torr and for the (14)N(16)O molecule in the range 100-300 Torr. The absorbance was also measured for individual rotational lines corresponding to the three modes of vibrations (upsilon(sub 1) - symmetric stretch, upsilon(sub 2) - symmetric bend, upsilon(sub 3) - anti-symmetric stretch) of the SO2 molecule in the pressure range 25-150 Torr. A graph of absorbance versus pressure was plotted for the observed rotational transitions of the three atmospherically significant molecules, and it was found that the absorbance was linearly proportional to the pressure range chosen, thereby validating Beer's law. The absorption cross-sections were determined from the graphical slopes for each rotational transition recorded for the HCl, NO and SO2 species. Qualitative and quantitative spectral changes in the FT-IR data will be discussed to identify and characterize various tubing materials with respect to their absorption features.

Haridass, C.↗

The determination of atmospheric trace gases using the correlation interferometer technique

The theoretical feasibility inherent in the correlation interferometry technique is demonstrated. High signal to noise and increased information content in a given partial interferogram are attractive features of the technique. The separation of interfering gas species is overcome by a precise measurement program for spectral line parameters of methane and other species. There are optical, mechanical, and electronic difficulties with the interferometry hardware design. Flight data from Cessna 402 over southeastern Virginia during April 1978 yielded amplitude fluctuations that are explainable only as internal nonlinearities. Misalignment of the AGC/interferometer optical axis also contributed to a large error source in the flight data. It is concluded that no useful data on gas burdens was obtained from these flights.

Kindle, E. C.↗

Atmospheric trace gases - Possibility of sources in the Southern Hemisphere

When measurements of globally distributed trace gases establish their existence in the Southern Hemisphere, it is not always clear whether their presence is due to transport from the Northern Hemisphere or partly from significant sources in the Southern Hemisphere. In this paper a simple criterion is developed whereby one can determine if significant Southern Hemisphere sources exist for a given trace gas. Despite the limitations of the model, there are strong indications that C2 hydrocarbons (C2H2, C2H4, C2H6), CO and CH4 have significant Southern Hemisphere sources.

Khalil, M. A. K.↗

Differences in the concentrations of atmospheric trace gases in and above the tropical boundary layer

Weekly air samples were collected at Cape Kumakahi (0 km) and at nearby Mauna Loa Observatory (3.4 km) which is above the boundary layer. EC/GC and GC/FID techniques were used to measure CH3I, CHCl3, CO and CH4 which are largely natural in origin, and C2Cl4, CCl4, CH3CCl3, (F-11), CCl2F2, (F-12), CHClF, (F-22) and C2F3Cl3 (F-113), which are due to anthropogenic (CCl3F) etc. activities. It was found that all these gases are significantly (alpha is equal to or less than 0.05) more abundant in the boundary layer than above it.

Rasmussen, R. A.↗