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At least 73 records · Page 4

Ambient formaldehyde detection with a laser spectrometer based on difference-frequency generation in PPLN

A laser spectrometer based on difference-frequency generation in periodically poled LiNbO3 (PPLN) has been used to quantify atmospheric formaldehyde with a detection limit of 0.32 parts per billion in a given volume (ppbV) using specifically developed data-processing techniques. With state-of-the-art fiber-coupled diode-laser pump sources at 1083 nm and 1561 nm, difference-frequency radiation has been generated in the 3.53-micrometers (2832-cm-1) spectral region. Formaldehyde in ambient air in the 1- to 10-ppb V range has been detected continuously for nine and five days at two separate field sites in the Greater Houston area operated by the Texas Natural Resource Conservation Commission (TNRCC) and the Houston Regional Monitoring Corporation (HRM). The acquired spectroscopic data are compared with results obtained by a well-established wet-chemical o-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA) technique.

NASA Discipline Life Sciences Technologies↗

A Hollow-Waveguide Gas Correlation Radiometer for Ultra-Precise Column Measurements of Formaldehyde on Mars

We present preliminary results in the development of a miniaturized gas correlation radiometer that implements a hollow-core optical fiber (hollow waveguide) gas correlation cell. The substantial reduction in mass and volume of the gas correlation cell makes this technology appropriate for an orbital mission -- capable of pinpointing sources of trace gases in the Martian atmosphere. Here we demonstrate a formaldehyde (H2CO) sensor and report a detection limit equivalent to approximately 30 ppb in the Martian atmosphere. The relative simplicity of the technique allows it to be expanded to measure a range of atmospheric trace gases of interest on Mars such as methane (CH4), water vapour (H2O), deuterated water vapour (HDO), and methanol (CH3OH). Performance of a formaldehyde instrument in a Mars orbit has been simulated assuming a 3 meter long, 1000 micron inner diameter hollow-core fiber gas correlation cell, a 92.8 degree sun-synchronous orbit from 400 km with a horizontal sampling scale of 10 km x 10 km. Initial results indicate that for one second of averaging, a detection limit of 1 ppb is possible.

Wilson, Emily L.↗

Toxicological Assessment of ISS Air Quality: September 2012 - October 2012 with Formaldehyde Supplement from May-October 2012

A summary of the analytical results from 6 grab sample containers (GSCs) and 12 pairs of formaldehyde badges collected on ISS and returned aboard 29S or 31 S is shown in an accompanying table. The average recoveries of the 3 surrogate standards from the GSCs were as follows: C-l3-acetone, 128%; fluorobenzene, 114%; and chlorobenzene, 78%. Recoveries of two lab-control formaldehyde badges averaged 95%.

James, John T.↗

Adsorption of Carbon Dioxide, Ammonia, Formaldehyde, and Water Vapor on Regenerable Carbon Sorbents

Results are presented on the development of reversible sorbents for the combined carbon dioxide, moisture, and trace‐contaminant (TC) removal for use in Extravehicular Activities (EVAs), and more specifically in the Primary Life Support System (PLSS). The currently available life support systems use separate units for carbon dioxide, trace contaminants, and moisture control, and the long‐term objective is to replace the above three modules with a single one. Furthermore, the current TC‐control technology involves the use of a packed bed of acid‐impregnated granular charcoal, which is nonregenerable, and the carbon‐based sorbent under development in this project can be regenerated by exposure to vacuum at room temperature. In this study, several carbon sorbents were fabricated and tested for simultaneous carbon dioxide, ammonia, formaldehyde, and water sorption. Multiple adsorption/vacuum‐regeneration cycles were demonstrated at room temperature, and also the enhancement of formaldehyde sorption by the presence of ammonia in the gas mixture.

Wojtowicz, Marek A.↗

A New Non-Resonant Laser-Induced Fluorescence Instrument for the Airborne in Situ Measurement of Formaldehyde

A new in situ instrument for gas-phase formaldehyde (HCHO), COmpact Formaldehyde FluorescencE Experiment (COFFEE), is presented. COFFEE utilizes nonresonant laser-induced fluorescence (NR-LIF) to measure HCHO, with 300 mW of 40 kHz 355 nm laser output exciting multiple HCHO absorption features. The resulting HCHO fluorescence is collected at 5 ns resolution, and the fluorescence time profile is fit to yield the ambient HCHO mixing ratio. Typical 1 sigma precision at approximately 0 pptv HCHO is 150 pptv for 1 s data. The compact instrument was designed to operate with minimal in-flight operator interaction and infrequent maintenance (1-2 times per year). COFFEE fits in the wing pod of the Alpha Jet stationed at the NASA Ames Research Center and has successfully collected HCHO data on 27 flights through 2017 March. The frequent flights, combined with a potentially long-term data set, makes the Alpha Jet a promising platform for validation of satellite-based column HCHO.

Nonresonant laser-induced fluorescenc↗

Development of a Photoacoustic Formaldehyde Monitor

Key indoor air quality pollutant formaldehyde (H2CO) 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 H2CO at low concentrations with data downlinked. Potential sources of H2CO 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 H2CO is 100 ppb for exposures of 7 days or longer. ISS concentrations recently run only 10 - 30 ppb but have spiked as high as 60 ppb in the past. Gateway real time monitoring requirements call for a range of 8 - 140 ppb. For this project, a concentration range of 5 - 500 ppb H2CO is targeted. The core tunable diode laser spectroscopy (TDLS) technology was developed by Vista Photonics through the NASA and US Navy Small Business Innovation Research (SBIR) programs. Monitors based on this technology have been demonstrated on ISS, trialed on a nuclear submarine and are in production as Anomaly Gas Analyzers for both ISS and Orion. Initially, direct absorption TDLS was used exclusively in these monitors, however, the H2CO target concentration is much lower, and a longer wavelength 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 monitor and explore potential adaptations for Gateway missions and beyond.

Paul D Mudgett↗

A21I-1875: Leveraging TEMPO Formaldehyde Observations to Assess Surface Air Quality

Surface ozone (O3) pollution is detrimental to human health, crop yields, and ecosystem productivity. Ground-based ozone observations are sparse and surface ozone retrievals from space are challenging. The process of producing ozone from the oxidation of volatile organic compounds (VOCs) in the presence of nitrogen oxides (NOx) results in formaldehyde (HCHO), which can be observed from satellite and by surface-based remote sensing. From limited field campaign observations, column formaldehyde has been shown to exhibit a strong relationship with surface ozone and, therefore, could be an useful proxy for detecting unmonitored regions of elevated ozone pollution. The spatiotemporal characteristics of this relationship are explored using ground-based Pandora spectrometers and airborne remote sensing data with surface ozone monitors across the United States during recent field campaigns over major cities (TRACER-AQ and STAQS). We extend our analysis to take advantage of HCHO column observations from recently launched Tropospheric Emissions: Monitoring of Pollution (TEMPO), a geostationary satellite over North America. TEMPO observations show preliminary promise in mapping regions of elevated surface ozone from space using column HCHO. We demonstrate the use of column HCHO in assessing the strength of the surface monitoring network, and in detecting the extent of regional ozone exceedances.

Prajjwal Rawat↗

Aqueous Phase Aldol Condensation of Formaldehyde and Acetone on Anatase TiO2(101) Surface: A Theoretical Investigation

A mechanistic understanding of catalytic reactions at solid-liquid interface is limited both experimentally and theoretically but attracts much interest. Using density functional theory calculations (DFT) and ab initio molecular dynamics (AIMD) simulations, we investigated the effect of liquid water on a-H abstraction, C-C coupling, and dehydration steps of aldol condensation of formaldehyde and acetone on an anatase TiO2(101) surface. The existence of the aqueous phase lowered the Gibbs energy of activation of dehydration step pronouncedly from 187 to 74 kJ/mol through proton transfer mechanism, making the hydrogenation pathway more favorable in the aqueous phase. In contrast, a mixed route prevails in the vapor phase. This work provides insights into the effect of the bulk water through a proton transfer mechanism on the dehydrogenation, C-C coupling, and dehydration

anatase TiO2, formaldehyde and acetone, aldol cond↗

Designing a Nanoscale Three-phase Electrochemical Pathway to Promote Pt-catalyzed Formaldehyde Oxidation

Gas-phase heterogeneous catalysis is a process spatially constrained on the two-dimensional surface of a solid catalyst. Here, we introduce a new toolkit to open up the third dimension. We discovered that the activity of a solid catalyst can be dramatically promoted by covering its surface with a nanoscale-thin layer of liquid electrolyte while maintaining efficient delivery of gas reactants, a strategy we call three-phase catalysis. Introducing the liquid electrolyte converts the original surface catalytic reaction into an electrochemical pathway with mass transfer facilitated by free ions in a three-dimensional space. Furthermore, we chose the oxidation of formaldehyde as a model reaction and observed a 25000-times enhancement in the turnover frequency of Pt in three-phase catalysis as compared to conventional heterogeneous catalysis. We envision three-phase catalysis as a new dimension for catalyst design and anticipate its applications in more chemical reactions from pollution control to the petrochemical industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Methanediol from cloud-processed formaldehyde is only a minor source of atmospheric formic acid

Atmospheric formic acid is severely underpredicted by models. A recent study proposed that this discrepancy can be resolved by abundant formic acid production from the reaction ( 1 ) between hydroxyl radical and methanediol derived from in-cloud formaldehyde processing and provided a chamber-experiment-derived rate constant, k 1 = 7.5 × 10 −12 cm 3 s −1 . High-level accuracy coupled cluster calculations in combination with E,J -resolved two-dimensional master equation analyses yield k 1 = (2.4 ± 0.5) × 10 −12 cm 3 s −1 for relevant atmospheric conditions ( T = 260–310 K and P = 0–1 atm). We attribute this significant discrepancy to HCOOH formation from other molecules in the chamber experiments. More importantly, we show that reversible aqueous processes result indirectly in the equilibration on a 10 min. time scale of the gas-phase reaction HCHO + H 2 O ⇌ HOCH 2 OH (2) with a HOCH 2 OH to HCHO ratio of only ca . 2%. Although HOCH 2 OH outgassing upon cloud evaporation typically increases this ratio by a factor of 1.5–5, as determined by numerical simulations, its in-cloud reprocessing is shown using a global model to strongly limit the gas-phase sink and the resulting production of formic acid. Based on the combined findings in this work, we derive a range of 1.2–8.5 Tg/y for the global HCOOH production from cloud-derived HOCH 2 OH reacting with OH. The best estimate, 3.3 Tg/y, is about 30 times less than recently reported. The theoretical equilibrium constant K eq (2) determined in this work also allows us to estimate the Henry’s law constant of methanediol (8.1 × 10 5 M atm −1 at 280 K).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formaldehyde Production from Isoprene Oxidation Across NOx Regimes

The chemical link between isoprene and formaldehyde (HCHO) is a strong, non-linear function of NOx (= 27 NO + NO2). This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the Southeast U.S., we quantify HCHO production across the urban-rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a "prompt" yield of HCHO (molecules of HCHO produced per molecule of freshly-emitted isoprene) and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons). Over the range of observed NOx values (roughly 0.1 - 2 ppbv), the prompt yield increases by a factor of 3 (from 0.3 to 0.9), while background HCHO increases by more than a factor of 2 (from 1.5 to 3.3 ppbv). We apply the same method to evaluate the performance of both a global chemical transport model (AM3) and a measurement-constrained 0-D chemical box model. Both models reproduce the NOx dependence of the prompt HCHO yield, illustrating that models with updated isoprene oxidation mechanisms can adequately capture the link between HCHO and recent isoprene emissions. On the other hand, both models under-estimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or under-estimated hydroxyl radical concentrations. Moreover, we find that the total organic peroxy radical production rate is essentially independent of NOx, as the increase in oxidizing capacity with NOx is largely balanced by a decrease in VOC reactivity. Thus, the observed NOx dependence of HCHO mainly reflects the changing fate of organic peroxy radicals.

VOC↗

Impact of Evolving Isoprene Mechanisms on Simulated Formaldehyde: An Inter-comparison Supported by in Situ Observations from SENEX

Isoprene oxidation schemes vary greatly among gas-phase chemical mechanisms, with potentially significant ramifications for air quality modeling and interpretation of satellite observations in biogenic-rich regions. In this study, in situ observations from the 2013 SENEX mission are combined with a constrained O-D photochemical box model to evaluate isoprene chemistry among five commonly used gas-phase chemical mechanisms: CBO5, CB6r2, MCMv3.2, MCMv3.3.1, and a recent version of GEOS-Chem. Mechanisms are evaluated and inter-compared with respect to formaldehyde (HCHO), a high-yield product of isoprene oxidation. Though underestimated by all considered mechanisms, observed HCHO mixing ratios are best reproduced by MCMv3.3.1 (normalized mean bias = -15%), followed by GEOS-Chem (-17%), MCMv3.2 (-25%), CB6r2 (-32%) and CB05 (-33%). Inter-comparison of HCHO production rates reveals that major restructuring of the isoprene oxidation scheme in the Carbon Bond mechanism increases HCHO production by only approx. 5% in CB6r2 relative to CBO5, while further refinement of the complex isoprene scheme in the Master Chemical Mechanism increases HCHO production by approx. 16% in MCMv3.3.1 relative to MCMv3.2. The GEOS-Chem mechanism provides a good approximation of the explicit isoprene chemistry in MCMv3.3.1 and generally reproduces the magnitude and source distribution of HCHO production rates. We analytically derive improvements to the isoprene scheme in CB6r2 and incorporate these changes into a new mechanism called CB6r2-UMD, which is designed to preserve computational efficiency. The CB6r2-UMD mechanism mimics production of HCHO in MCMv3.3.1 and demonstrates good agreement with observed mixing ratios from SENEX (-14%). Improved simulation of HCHO also impacts modeled ozone: at approx. 0.3 ppb NO, the ozone production rate increases approx. 3% between CB6r2 and CB6r2-UMD, and rises another approx. 4% when HCHO is constrained to match observations.

isoprene↗

Glyoxal Yield from Isoprene Oxidation and Relation to Formaldehyde: Chemical Mechanism, Constraints from SENEX Aircraft Observations, and Interpretation of OMI Satellite Data

Glyoxal (CHOCHO) is produced in the atmosphere by the oxidation of volatile organic compounds(VOCs). Like formaldehyde (HCHO), another VOC oxidation product, it is measurable from space by solar backscatter. Isoprene emitted by vegetation is the dominant source of CHOCHO and HCHO in most of the world. We use aircraft observations of CHOCHO and HCHO from the Southeast Nexus (SENEX) campaign over the southeast US in summer 2013 to better understand the CHOCHO time-dependent yield from isoprene oxidation, its dependence on nitrogen oxides (NO (sub x) triple bonded to NO plus NO2), the behavior of the CHOCHO-HCHO relationship, the quality of Ozone Monitoring Instrument (OMI) CHOCHO satellite observations, and the implications for using CHOCHO observations from space as constraints on isoprene emissions. We simulate the SENEX and OMI observations with the Goddard Earth Observing System chemical transport model (GEOSChem) featuring a new chemical mechanism for CHOCHO formation from isoprene. The mechanism includes prompt CHOCHO formation under low-NO (sub x) conditions following the isomerization of the isoprene peroxy radical (ISOPO2).The SENEX observations provide support for this prompt CHOCHO formation pathway, and are generally consistent with the GEOS-Chem mechanism. Boundary layer CHOCHO and HCHO are strongly correlated in the observations and the model, with some departure under low-NO (sub x) conditions due to prompt CHOCHO formation. SENEX vertical profiles indicate a free-tropospheric CHOCHO background that is absent from the model. The OMI CHOCHO data provide some support for this free-tropospheric background and show southeast US enhancements consistent with the isoprene source but a factor of 2 too low. Part of this OMI bias is due to excessive surface reflectivities assumed in the retrieval. The OMI CHOCHO and HCHO seasonal data over the southeast US are tightly correlated and provide redundant proxies of isoprene emissions. Higher temporal resolution in future geostationary satellite observations may enable detection of the prompt CHOCHO production under low-NO (sub x) conditions apparent in the SENEX data.

OMI↗

Wintertime Formaldehyde: Airborne Observations and Source Apportionment Over the Eastern United States

Formaldehyde (HCHO) is generated from direct urban emission sources and secondary production from the photochemical reactions of urban smog. HCHO is linked to tropospheric ozone formation, and contributes to the photochemical reactions of other components of urban smog. In this study pollution plume intercepts during the Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) campaign were used to investigate and characterize the formation of HCHO in relation to several anthropogenic tracers. Analysis of aircraft intercepts combined with detailed chemical box modeling downwind of several cities suggest that the most important contribution to observed HCHO was primary emission. A box model analysis of a single plume suggested that secondary sources contribute 21±10% of observed HCHO. Ratios of HCHO/CO observed in the northeast U.S., from Ohio to New York, ranging from 0.2-0.6%, are consistent with direct emissions combined with at most modest photochemical production. Analysis of the nocturnal boundary layer and residual layer from repeated vertical profiling over urban influenced areas indicate a direct HCHO emission flux of 1.3 x 10 14 molecules cm -2 h -1 . In a case study in Atlanta, GA, nighttime HCHO exhibited a ratio to CO (0.6 – 1.8%) and was anti-correlated with O 3 . Observations were consistent with mixing between direct HCHO emissions in urban air masses with those influenced by more rapid HCHO photochemical production. The HCHO/CO emissions ratios determined from the measured data are 2.3 - 15 times greater than the NEI 2017 emissions database. The largest observed HCHO/CO was 1.7 – 1.8%, located near co-generating power stations.

Formaldehyde↗

Atmospheric Formaldehyde Trend and Its Source Attributions in the Recent Decades

Formaldehyde (CH 2 O) is one of the most important reactive trace gases in the atmosphere with an important role in tropospheric chemistry and in the control of surface air quality. Sources of CH 2 O includes direct emissions and in situ production from the oxidation of volatile organic compounds (VOCs). In this study, we investigate spatial-temporal variations in atmospheric CH 2 O and how changes in CH 2 O couple with tropospheric ozone variability during the past two decades using recently available retrievals from the Ozone Monitoring Instrument (OMI) aboard NASA’s Aura satellite and the RefD1 simulation from the NASA Goddard Earth Observing System Chemistry Climate Model (GEOSCCM). Our initial analysis provides evidence of significant increases in atmospheric CH 2 O concentrations over several of the world’s major anthropogenic regions, including China, India, and the Middle East, and several biomass burning regions, including South America, southern Africa, boreal regions and Indonesia. We furthermore will identify regional source contributions to CH 2 O trends, including anthropogenic VOCs emissions, biogenic isoprene emissions and open fires. In particular, we will focus on anthropogenic emission regions to examine the role of changing anthropogenic VOC emissions on CH 2 O abundance.

Atmospheric Formaldehyde↗