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NASA NTRSDate not supplied

Development of a Photoacoustic Formaldehyde Monitor

Key indoor air quality pollutant formaldehyde (H 2 CO) is tracked on International Space Station (ISS) using passive badges returned to the ground periodically for analysis. The process is time-consuming both in preparation and for analysis upon return 6-12 months later. Badges also require precious crew time for deploy, retrieval and stow. As NASA’s focus in space exploration shifts to the Moon and Mars, archival sample return becomes increasingly impractical, so the aim of this project is to develop a highly reliable real-time analyzer for H 2 CO at low concentrations with data downlinked. Potential sources of H 2 CO include materials off gassing, use of formalin as a tissue fixative in biological payloads and overheating of acetal polymers. The Spacecraft Maximum Allowable Concentration (SMAC) for H 2 CO in air is 100 ppb for exposures of 7 days or longer. ISS concentrations of H 2 CO are running only 10 - 30 ppb in the recent several years but have spiked as high as 60 ppb. Gateway real time monitoring requirements for H 2 CO call for a range of 8 - 138 ppb. For this project, a concentration range of 5 - 500 ppb H 2 CO is targeted. The core tunable diode laser spectroscopy (TDLS) technology used for this project was developed by Vista Photonics through the NASA and US Navy Small Business Innovation Research (SBIR) programs. Monitors based on TDLS have been demonstrated on ISS, trialed on a nuclear submarine and are being certified as portable Anomaly Gas Analyzers (AGA) for both ISS and Orion. Initially, direct absorption TDLS was used exclusively in these devices. The H 2 CO target concentration, however, is low ppb, and a longer wavelength is required, so a photoacoustic spectroscopy (PAS) technique was adapted, where the laser excitation is detected by a sensitive microphone vs. a conventional photodetector. This paper will discuss the results of NASA-JSC laboratory testing of a prototype PAS based formaldehyde in air monitor and briefly discuss next steps.

Photoacoustic Formaldehyde Monitor↗
DOE OSTI2023

Isotope effect in formaldehyde steam reforming on Pt/m-ZrO 2 : Insight into chemical promotion by alkalis

Infrared spectroscopy, temperature programmed reaction mass spectrometry (TP-reaction/MS), and catalyst testing were used to investigate alkali promotion of dehydrogenation selectivity during formaldehyde steam reforming (FSR) on Pt/m-ZrO 2 . In a preferred pathway, formaldehyde reacts with water forming hydrogen and formate, followed by forward formate decomposition to CO 2 and H 2 . Alkali-doping of 2 wt% Pt/m-ZrO 2 increases catalyst basicity, which weakens the formate C-H bond promoting formate dehydrogenation / decarboxylation. Promotion by alkali in FSR was observed through a formate nu(CH) band shift to lower wavenumbers in infrared spectroscopy, and through a decrease in the normal isotope effect in switching from H-to D-labeled formalde-hyde in TP-reaction/MS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Enhanced CO 2 Adsorption Capacity in Highly Porous Carbon Materials Derived from Melamine-Formaldehyde Resin

Here, the present study explores the synthesis of N-doped carbon materials with large surface porosity using commercial melamine-formaldehyde resin as the precursor and KOH as the activator. The resin was carbonized first and then activated by KOH with varying KOH amount and activation temperature. Notably, the as-obtained sorbents display advanced porosity with the highest surface area and pore volume of 1591 m 2 /g and 0.74 cm 3 /g, respectively, along with high N content ranging from 6.43 to 18.34 wt %. Remarkably, maximum CO 2 capture amounts of 5.42 and 3.52 mmol/g were accomplished at 0 and 25 degrees C, 1 bar for as-synthesized carbons. Systematic studies point out that narrow microporosity is the major factor determining the CO 2 uptake of these carbons under ambient pressure. Furthermore, these sorbents display notable CO 2 selectivity, rapid adsorption kinetics, moderate heat of adsorption, substantial dynamic CO 2 capture capacity, and stable recyclability. These results underscore the potential of melamine-formaldehyde resin-derived N-doped porous carbon as an efficient and versatile adsorbent for CO 2 capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

A formaldehyde and nitrogen dioxide toxics monitor for environmental justice

DOE’s Integrated Field Laboratories (IFLs) require a vast array of measurements to measure urban air quality. Nitrogen dioxide (NO2) and formaldehyde (HCHO) are ubiquitous pollutants with numerous sources, most notably vehicle exhaust. High-spatial density measurements are critical to understanding how certain neighborhoods are more adversely impacted by pollutants. This report describes the results of a Phase I SBIR project to develop and demonstrate a rapid, affordable, low-power monitor to provide high spatial resolution mobile measurements of formaldehyde and nitrogen dioxide at street-level, where people live and walk. The spatial density will be achieved via rapid measurements on a mobile platform. This sensor will quantify spatial disparities in cities of the toxics, HCHO and NO2, as well as carbon monoxide and carbon dioxide for better source identification. These species are detected in the mid infrared by laser absorption spectroscopy, and fiberoptics are used. Tasks accomplished include identification and testing of the appropriate spectroscopic regions; coupling of laser light into a fiberoptic system; development of software to control miniature electronics to scan and control two lasers simultaneously; coupling of the mid infrared fiber into a multipass cell for enhanced pathlength and sensitivity; characterization of sources of instrument noise; and design work for a Phase II prototype.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2016

Injection Seeded Laser for Formaldehyde Differential Fluorescence Lidar

We describe the design and development of an injection seeded Nd:YVO4 laser for use in a differential fluorescence lidar for measuring atmospheric formaldehyde profiles. A high repetition rate Q-switched laser is modified to accept injection seed input to spectrally narrow and tune the output. The third harmonic output is used to excite formaldehyde (HCHO) fluorescence when tuned to a HCHO absorption line. Spectral confirmation is made with the use of a photoacoustic cell and grating spectrometer.

formaldehyde (HCHO) fluorescence↗
NASA NTRS2019

Explicit Aerosol Correction of OMI Formaldehyde Retrievals

Atmospheric aerosols are significant sources of uncertainty in air mass factor (AMF) calculations for trace gas retrievals using ultraviolet measurements from space. Current trace gas retrievals typically do not consider aerosols explicitly as cloud products partially account for aerosol effects. Here, we propose a new measurement-based approach to correct for aerosols explicitly in the AMF calculation, apply it to Ozone Monitoring Instrument (OMI) formaldehyde (HCHO) retrievals and quantify the aerosol-induced HCHO vertical column density difference for three aerosol types (smoke, dust, and sulfate) during 2006–2007. We use OMI aerosol retrievals for aerosol optical properties and vertical profiles to construct lookup tables of scattering weights as functions of geometry, surface pressure, surface albedo, and aerosol information. The average difference between the National Aeronautics and Space Administration operational OMI HCHO product (not considering aerosols) and the results obtained in this study on a global scale are 27%, 6%, and −0.3% for smoke, dust, and sulfate aerosols, respectively. The region with the largest aerosol effects is East China, where the explicit smoke aerosol correction enhances mean HCHO vertical column densities by 35%, with corrections to individual observations sometimes larger than 100%. The quantified aerosol effects are applicable under clear-sky conditions. This study highlights the need to implement aerosol corrections in the AMF calculation for HCHO retrievals. This is particularly relevant in regions with high levels of pollution where aerosols interfere the most with formaldehyde satellite observations.

Ozone Monitoring Instrument (OMI) formaldehyde (HC↗
NASA NTRS1971

Photoionization of methanol and formaldehyde

Photoions produced in methanol and formaldehyde by radiation in the spectral region 450-1150 A were analyzed mass spectrometrically, and their relative yields were determined as a function of wavelength. First ionization potentials were determined, and the ion yield curves were interpreted in terms of ionization processes in conjunction with other data. Fragment ions were detected on mass numbers of 31, 30, 29, 15, and 14 for methanol, and 29, 2, and 1 for formaldehyde. The associated appearance potentials were determined and were used to calculate heats of formation of the ions CH2OH(+) and HCO(+), and the radicals CH3, CH2, and HCO.

Warneck, P.↗
NASA NTRS1972

Survey of molecular lines near the galactic center. I - 6-centimeter formaldehyde absorption in Sagittarius A, Sagittarius B2, and the galactic plane from 359.4 to 2.2 deg galactic longitude.

The data obtained indicate that the formaldehyde is concentrated in distinct clouds to a much greater extent than atomic hydrogen. The findings suggest that most of the mass in these clouds is in the form of molecular hydrogen. The locations of four dominant clouds are reported. The strongest formaldehyde features are apparently associated with the galactic nucleus. Estimates of the hydrogen density in the clouds, based on the assumption of stability and also on a comparison with local dark clouds, indicate a number density in the range from 1000 to 10,000 per cc, and a mass of approximately 500,000 solar masses.

Scoville, N. Z.↗
NASA NTRS1976

The reactions of O(ID) and OH with CH3OH, oxidation of the HCO radial, and the photochemical oxidation of formaldehyde

An experimental, laboratory study of the various photochemical reactions that can occur in the mesosphere and stratosphere is presented. N2O was photolyzed at 2139 A in the presence of CH3OH and CO. The O(id) produced in the photolysis reacted with CH3OH to produce OH radicals, and thus the reactions of both O(id) and OH were able to be studied. Also considered was the oxidation of the HCO radical. Mixtures of Cl2, O2, H2CO, and sometimes N2 or He were irradiated at 3660 A at several temperatures to photodecompose the Cl2. The photochemical oxidation of formaldehyde was studied as follows: formaldehyde in the presence of N2 and/or O2 (usually dry air) was photolyzed with a medium pressure Hg lamp used in conjunction with various filters which transmit different relative amounts of Hg lines from 2894 A to 3660 A. Results are presented and discussed, along with a description of experimental procedures and apparatus, and chemical reaction kinetics.

Osif, T. L.↗
NASA NTRS1986

A new technique for collection, concentration and determination of gaseous tropospheric formaldehyde

This article describes an improved technique for making in situ measurements of gaseous tropospheric formaldehyde (CH2O). The new technique is based on nebulization/reflux principles that have proved very effective in quantitatively scrubbing water soluble trace gases (e.g., CH2O) into aqueous mediums, which are subsequently analyzed. Atmospheric formaldehyde extractions and analyses have been performed with the nebulization/reflux concentrator using an acidified dinitrophenylhydrazine solution that indicate that quantitative analysis of CH2O at global background levels (about 0.1 ppbv) is feasible with 20-min extractions. Analysis of CH2O, once concentrated, is accomplished using high performance liquid chromatography with ultraviolet photometric detection. The CH2O-hydrazone derivative, produced by the reaction of 2,4-dinitrophenylhydrazine in H2SO4 acidified aqueous solution, is detected as CH2O.

Cofer, W. R., III↗
NASA NTRS1987

A survey of formaldehyde in high Galactic latitudes

The discovery of formaldehyde (H2CO) in four out of 15 CO-clouds observed in high Galactic latitudes is reported. For one of these a velocity-integrated formaldehyde map is presented. The clouds are clearly connected to CO clouds described by de Vries et al. (1986), to Lynds bright and dark nebulae (Lynds, 1963), and to the Galactic infrared cirrus (Low et al., 1984). The distribution of CO and H2CO clouds is compared. The depths of the l(10-11)H2CO lines show no correlation to the integrated J = l-0(C-12)O line intensities.

Heithausen, A.↗
NASA NTRS1990

Observations of formaldehyde in Comet Machholtz (1988j)

Comet Machholtz's 1(11)-1(10) formaldehyde emission was detected with the VLA in September, 1988 at 6-cm wavelength; the small blueshift of -0.76 + or - 0.40 km/sec noted by these observations is consistent with an anisotropic outgassing of the cometary nucleus in the solar direction. The derived formaldehyde production rate for Comet Halley, which exhibits a similar emission line blueshift, was 1.5 x 10 to the 28th mol/sec, while for Comet Machholtz the production rate is about an order of magnitude higher, at 2 x 10 to the 29th mol/sec. The fading of Comet Machholtz after these observations is ascribed to its breakup.

Snyder, Lewis E.↗
NASA NTRS1990

VLA searches for formaldehyde and cyanoacetylene emission from comet P/Brorsen-Metcalf (1989o)

In Sep. 1989, Very Large Array (VLA) searches were conducted for both formaldehyde (H2CO) and cyanoacetylene (HC3N) emission from Comet P/Brorsen-Metcalf (1989o). In early July, this comet was outgassing strongly at a brighter than average preperihelion rate, and the hope was that it would continue to do so through perihelion. By observing the 1 sub 11 to 1 sub 10 transition of H2CO at 4,829.659 MHz (6 cm lambda) during the phase of maximum outgassing, it was expected that spectra would be collected with a high signal to noise ratio which would show the temporal behavior of formaldehyde relative to other molecules. During this same observation period, a search was also made for the J-1-0, F-2-1 rotational transition of cyanoacetylene at 9098.3321 MHz (3.3 cm lambda).

Snyder, Lewis E.↗
NASA NTRS1991

Collisional excitation of formaldehyde in 'hot' interstellar molecular regions

Earlier calculations for rotational excitation of formaldehyde by collisions with He atoms are extended to include the lowest 81 rotational levels and kinetic temperatures to 300 K. Calculations are generally based on Green et al. (1978) but coupled differential equations are solved via a modified log-derivative propagator at low energies (Manolopoulos, 1986) and an R-matrix propagator at higher energies (Stechel, Walker, and Light, 1978). Consideration is given to the expected accuracy of the rates for excitation of formaldehyde by collisions with He atoms which are calculated in the present paper and to the expected differences between these rates and those for excitation by H2 molecules which comprise a larger fraction of the interstellar gas. The comparisons performed indicate that, for excitation by He, calculated state-to-state rates are likely to be 50 percent accurate, and total excitation rates, better than 20 percent. For excitation by H2, the rates should be increased by a factor of 2.2.

Green, Sheldon↗
NASA NTRS1991

Formaldehyde in envelopes of interstellar dark clouds

Observed formaldehyde column densities of 1 x 10 to the 12th - 3 x 10 to the 13th/sq cm in cloud envelopes along lines of sight with A(V) = 1-4 mag can not be explained with the current understanding of interstellar gas phase chemistry. However, these column densities can be reproduced by a simple time-dependent model in which H2CO is supplied to the gas phase by the erosion of icy grain mantles. The release of H2CO from the grain mantles must occur on time scales comparable to the time scales for mixing from the cloud interior to the cloud envelope. Thus, in low-density regions of clouds, it appears that formaldehyde is the second molecule whose gas phase source is primarily ejection from grains. This simple model suggests understanding gas phase steady state in clouds on macroscopic, rather than microscopic, spatial scales.

Federman, S. R.↗
NASA NTRS1991

Sources and geochemical evolution of cyanide and formaldehyde

The major source of cyanide has, in current paleoatmospheric models, been assumed to be the reaction of photodissociated thermospheric nitrogen with a limiting supply of stratospheric methane. Formaldehyde may be produced with more ease from an atmosphere of carbon dioxide as the dominant carbon species, and from carbonate in solution or sorbed in double layer hydroxide minerals. Potentially more important sources for cyanide and other carbon containing molecules are the partially photoprotected northern and southern auroral ovals where continuous currents reaching several mega-amperes induce ion-molecule reactions, extending into the lower stratosphere. In simulated environments of this kind, the cyanide ion is known to be produced from oxidized carbon species potentially more abundant than methane. Rainout of cyanide and formaldehyde place them in two different geochemical reaction reservoirs. In the anoxic Archean hydrosphere, about 1mM in Fe2(+), the cyanide ion would have been efficiently converted to the stable ferrocyanide complex Fe(CN) sub 6(4-), protecting it from the commonly considered fate of decomposition by hydrolysis, and eventually incorporating it in pyroaurite type minerals, most efficiently in green rust where it converts to insoluble ferriferrocyanide, prussian blue.

Arrhenius, G.↗
NASA NTRS1995

Very low temperature formaldehyde reactions and the build-up of organic molecules in comets and interstellar ices

We have investigated thermally promoted reactions of formaldehyde (H2CO) in very low temperature ices. No such reactions occurred in ices of pure formaldehyde. However, addition of trace amounts of ammonia (NH3) were sufficient to catalyze reactions at temperatures as low as 40 K. Similar reactions could take place in interstellar ices and in Comets and produce considerable amounts of organic molecules.

Schutte, W. A.↗
NASA NTRS1993

Tentative identification of formaldehyde in the Martian atmosphere

Solar occultation observations of the Martian atmosphere near the limb of the planet were performed during the Phobos mission by means of the Auguste infrared spectrometer in the ranges 2707-2740 and 5392-5272/cm with a resolving power of approximately = 1300. The spectra exhibit features at 2710 and 2730/cm which have not been identified previously. After applying a set of corrections to the data and examining the spectra of various molecules, we are led to conclude that the best candidate for the above-mentioned features is formaldehyde (CH2O). It was observed in eight of the nine successful occultation sequences, mainly between 8 and 20 km with an average mixing ratio of 0.5 (+0.8, - 0.3) ppm (there are no good data below 8 km). The observations are performed in equatorial spring conditions. The altitude distribution of formaldehyde reveals correlation with the permanent haze opacity.

Korablev, O. I.↗